Coating composition, coating film, laminate, and process for production of laminate

ABSTRACT

[Problem to be Solved] 
     Provided is a coating composition excellent in antifouling properties, transparency and hydrophilicity and capable of maintaining surface hydrophilicity even at high temperature. 
     [Solution] 
     A coating composition containing
         (A) a metal oxide particle having a number average particle size of 1 nm to 400 nm, and   (B) a polymer particle,   in which the content of an aqueous-phase component in the component (B), represented by the following expression (I), is 20 mass % or less.       

       The content of the aqueous-phase component (%)=(dry mass of a filtrate obtained by filtering the component (B) at a molecular cutoff of 50,000)×(100−total mass of solid content)/(mass of the filtrate−dry mass of the filtrate)×100/the total mass of solid content  (I).

TECHNICAL FIELD

The present invention relates to a coating composition, a coating film,a laminate and a method for manufacturing the laminate. Morespecifically, the present invention relates to a coating composition, acoating film, a laminate and a method for manufacturing the laminate,and a solar cell module, a reflector device and a solar thermal powergeneration system using these.

BACKGROUND ART

Recently, environmental consciousness has been increased by a globalwarming phenomenon and a novel energy system generating no greenhousegases such as carbon dioxide gas has attracted attention.Environment-friendly recyclable energy such as photovoltaic powergeneration and wind power generation does not emit gases, which are saidto induce global heating, such as carbon dioxide gas, it has beenactively studied as clean energy. A solar cell and solar thermal powergeneration have attracted attention because of excellent safety andeasy-to-handle.

As a typical solar thermal power generation method, there are a centralsystem (central tower system), a distributed system (parabolic trough)and a dish/stirling system. In these systems, sunlight is collected to aspot by use of a reflecting mirror and heat of sunlight harvested isconverted into electric energy through thermoelectric conversion. Whilethe key point of this system is collecting light without loss, as thefactor significantly varying efficiency, a reduction of reflectivitycaused by stain of a reflecting mirror is particularly concerned as aproblem. Furthermore, a solar cell whose light-receiving surface isprotected by a protecting cover formed of glass, a weather-resistantresin film and the like, has an analogous problem of reducing the lighttransmittance and thus an energy conversion efficiency of the solar cellsince the protecting cover is stained with smoke dust during long-termuse.

As a technique for preventing surface stain, for example, PatentLiterature 1 discloses a technology for forming a surface layer byapplying a coating liquid, which contains tungstic acid dissolved inammonia water and distilled water, onto a layer containing an anatasetype titanium oxide, and then baking at 700° C. to obtain a layer formedof tungsten oxide. Furthermore, an attempt to improve antifoulingproperties and the like by blending not only an inorganic component butalso an organic component has been made.

CITATION LIST Patent Literature

-   Patent Literature 1: Japanese Patent Application Laid-Open No.    10-114545

SUMMARY OF INVENTION Technical Problem

However, conventional coating compositions including Patent Literature 1have much to be improved. The technology disclosed in Patent Literature1 has a problem of cracking and peeling off easily occurred at a coatingfilm in the case that the resultant coating film is formed on thesurface of a large-scale reflecting mirror and the like used in a solarcell module and the like since only inorganic components are blended.

Furthermore, coating compositions containing not only inorganiccomponents but also organic components still have much to be improvedwith respect to properties such as antifouling properties, transparencyand hydrophilicity. Furthermore, in the case that such a coating film isplaced under high-temperature conditions such as desert, a problem suchas significant reduction of antifouling properties by breeding out of anaqueous-phase component in the surface of the coating film, and thelike.

The present invention was made in the aforementioned circumstances, andone object of the present invention is to provide a coating compositionexcellent in antifouling properties, transparency and hydrophilicity andcapable of maintaining surface hydrophilicity even at high temperature.

Solution to Problem

The present inventors have intensively conducted studies with a view tosolving the aforementioned problems. As a result, they found that theaforementioned problems can be overcome by preparing a coatingcomposition comprising (A) a metal oxide particle having a numberaverage particle size of 1 nm to 400 nm and (B) a polymer particle andhaving a predetermined content or less of an aqueous-phase component,and based on the finding, the present invention was achieved.

More specifically, the present invention is as follows:

[1]

A coating composition comprising

(A) a metal oxide having a number average particle size of 1 nm to 400nm, and

(B) a polymer particle,

wherein the content of an aqueous-phase component in the component (B),represented by the following expression (I), is 20 mass % or less:

The content of the aqueous-phase component (%)=(dry mass of a filtrateobtained by filtering the component (B) at a molecular cutoff of50,000)×(100−total mass of solid content)/(mass of the filtrate−dry massof the filtrate)×100/the total mass of solid content  (I).

[2]

The coating composition according to item [1], wherein

the component (B) is a polymer emulsion particle (B1) obtained in apolymerization material solution comprising

a component (b1): a hydrolyzable silicon compound,a component (b2): a vinyl monomer,a component (b3): an emulsifier, anda component (b4): water,by polymerizing the component (b1) and the component (b2).[3]

The coating composition according to item [1] or [2], wherein thecontent of the aqueous-phase component is 15 mass % or less.

[4]

The coating composition according to any one of items [1] to [3],wherein the component (B) has a number average particle size of 10 nm to800 nm.

[5]

The coating composition according to any one of items [2] to [4],wherein the component (b2) is a vinyl monomer having at least onefunctional group selected from the group consisting of a hydroxy group,a carboxyl group, an amide group, an amino group and an ether group.

[6]

The coating composition according to any one of items [2] to [5],wherein a mass ratio ((b2)/(B)) of the component (b2) to the component(B) is 0.01/1 to 1/1.

[7]

The coating composition according to any one of items [2] to [6],wherein a mass ratio ((b2)/(A)) of the component (b2) to the component(A) is 0.01/1 to 1/1.

[8]

The coating composition according to any one of items [1] to [7],wherein the component (B) has a core/shell structure comprising a corelayer and one or two or more shell layers covering the core layer.

[9]

The coating composition according to item [8], wherein a mass ratio((b2)/(b1)) of the component (b2) to the component (b1) in the corelayer is 0.01/1 to 1/1, and

the mass ratio ((b2)/(b1)) of the component (b2) to the component (b1)in an outermost layer of the shell layers is 0.01/1 to 5/1.

The coating composition according to any one of items [2] to [9],wherein the component (B) is a polymer emulsion particle obtained bypolymerizing the polymerization material solution in the presence of aseed particle forming the core layer, and

the seed particle is obtained by polymerizing at least one componentselected from the group consisting of the component (b1), the component(b2) and a component (b5): another vinyl monomer copolymerizable withthe component (b2).

[11]

The coating composition according to any one of items [2] to [10],wherein the component (b2) is a vinyl monomer having a secondary amidegroup, a tertiary amide group or both of those.

The coating composition according to any one of items [1] to [11],wherein a mass ratio ((A)/(B)) of the component (A) to the component (B)is 110/100 to 480/100.

[13]

The coating composition according to any one of items [1] to [12],further comprising a component (C): at least one hydrolyzable siliconcompound selected from the group consisting of compounds represented bythe following formulas (1), (2) and (3):

R¹ _(n)SiX_(4-n)  (1)

wherein R¹ represents a hydrogen atom, or an alkyl group, alkenyl group,alkynyl group or aryl group having 1 to 10 carbon atoms and optionallyhaving a halogen group, a hydroxy group, a mercapto group, an aminogroup, a (meth)acryloyl group or an epoxy group; X represents ahydrolyzable group; and n is an integer of 0 to 3.

X₃S¹—R² _(n)—SiX₃  (2)

wherein X represents a hydrolyzable group; R² represents an alkylenegroup or phenylene group having 1 to 6 carbon atoms; and n is 0 or 1.

R³—(O—Si (OR³)₂)_(n)—OR³  (3)

wherein R³ represents an alkyl group having 1 to 6 carbon atoms; and nis an integer of 2 to 8.[14]

The coating composition according to item [13], wherein a mass ratio((C)/(A)) of the component (C) to the component (A) is 1/100 to 150/100.

[15]

The coating composition according to any one of items [1] to [14],wherein the component (B) has a number average particle size of 10 nm to100 nm.

[16]

The coating composition according to any one of items [1] to [15],wherein the component (A) comprises,

a component (A1): silica having a number average particle size of 1 nmto 400 nm, and

a component (A2): an infrared absorbent having a number average particlesize of 1 nm to 2000 nm;

a mass ratio ((A1+ A2)/(B)) of a total content of the component (A1) andthe component (A2) to a content of the component (B) is 60/100 to1000/100; and

a mass ratio ((A2)/(A1+B)) of the content of the component (A2) to atotal content of the component (B) and the component (A1) is 0.05/100 to40/100.

[17]

The coating composition according to any one of items [1] to [16],wherein the component (A) comprises

a component (A1): silica having a number average particle size of 1 nmto 400 nm, and

a component (A3): a photocatalyst having a number average particle sizeof 1 nm to 2000 nm;

a mass ratio ((A1+A3)/(B)) of a total content of the component (A1) andthe component (A3) to a content of the component (B) is 60/100 to480/100; and

a mass ratio ((A1)/(A1+A3)) of a content of the component (A1) to thetotal content of the component (A1) and the component (A3) is 85/100 to99/100.

[18]

The coating composition according to any one of items [1] to [17] forantireflection.

[19]

The coating composition according to any one of items [1] to [17] forsolvent resistance.

[20]

The coating composition according to any one of items [1] to [17] forantistatic use.

[21]

The coating composition according to any one of items [1] to [17] forheat resistance.

[22]

The coating composition according to any one of items [1] to [17] forhard coating.

[23]

A coating film obtained from the coating composition according to anyone of items [1] to [22].

[24]

A coating film comprising

(A) a metal oxide having a number average particle size of 1 nm to 400nm, and

(B) a polymer particle surrounded by the component (A),

wherein a film formed of a component (B2) having a molecular cutoff of50,000 or less and extracted from the component (B) by ultrafiltrationhas a surface water contact angle of 30° or less.[25]

A coating film comprising

(A) a metal oxide having a number average particle size of 1 nm to 400nm, and

(B) a polymer particle surrounded by the component (A),

wherein a film formed of a component (B2) having a molecular cutoff of50,000 or less and extracted from the component (B) by ultrafiltrationhas a surface water contact angle of more than 30° and the contentthereof is 5 mass % or less.[26]

The coating film according to item [24] or [25], wherein the component(B) is an emulsion particle.

[27]

The coating film according to any one of items [23] to [26], having asurface water contact angle at 20° C. of 30° or less.

[28]

The coating film according to any one of items [23] to [27], wherein thecoating film after a high-temperature/high-humidity test in which thecoating film is allowed to stand still for 24 hours under the conditionsof a temperature of 90° C. and a humidity of 90% has a surface watercontact angle of 20° or less.

[29]

A laminate having

a substrate and a coating film obtained by applying the coatingcomposition according to any one of items [1] to [22] or the coatingfilm according to any one of items [23] to [28] and formed on at leastone of surfaces of the substrate.

[30]

The laminate according to item [29], having a light transmittance higherthan a light transmittance of the substrate.

[31]

The laminate according to item [29] or [30], wherein the coating filmhas a refractive index 0.1 or more lower than a refractive index of thesubstrate.

[32]

The laminate according to any one of items [29] to [31], wherein thecoating film has two or more layers.

[33]

The laminate according to any one of items [29] to [32], wherein anoutermost layer positioned on an opposite side of the substrate has arefractive index 0.1 or more lower than a refractive index of a layeradjacent to the outermost layer.

[34]

The laminate according to item [32] or [33], wherein layers constitutingthe coating film each have a thickness (dn) of 10 nm to 800 nm and atotal thickness (Σdn) of the coating film is 100 nm to 4000 nm.

[35]

The laminate according to any one of items [29] to [34], wherein thesubstrate has a light transmittance of 30% to 99%.

[36]

The laminate according to any one of items [29] to [35], wherein a ratio((Rc)/(Rb)) of a reflectivity (Rc) of an opposite surface to thesubstrate of the coating film to a reflectivity (Rb) of the surface ofthe substrate on a coating film side is 98% or more.

[37]

The laminate according to any one of items [29] to [36], wherein thedifference in refractive index between the coating film and thesubstrate is 0.2 or less.

[38]

The laminate according to any one of items [29] to [37], wherein thecoating film has a refractive index of 1.30 to 1.48.

[39]

The laminate according to any one of items [36] to [38], wherein thesurface of the substrate on the coating film side has the reflectivity(Rb) of 80% or more.

[40]

The laminate according to any one of items [29] to [39], wherein thesubstrate comprises at least one substance selected from the groupconsisting of glass, an acrylic resin, a polycarbonate resin, a cyclicolefin resin, a polyethylene terephthalate resin and anethylene-fluoroethylene copolymer.

[41]

A method for manufacturing a laminate, comprising the steps of:

forming a coating film by applying the coating composition according toany one of items [1] to [22] on at least one of surfaces of a substrate,and

applying at least one of a thermal treatment at 70° C. or more and apressurization treatment at 0.1 kPa or more to the coating film.

[42]

The laminate according to any one of items [29] to [40], which is amember for use in an energy conversion apparatus.

[43]

The laminate according to item [42], which is a protective member for asolar cell module.

[44]

A solar cell module comprising

the laminate according to item [42],

a backsheet arranged so as to face the laminate, and

an electric power generating element arranged between the laminate andthe backsheet.

[45]

The laminate according to item [42], which is a protective member for alight reflecting mirror.

[46]

A reflector device having

a light reflecting mirror,

the laminate according to item [45] for protecting a reflection surfaceof the light reflecting mirror, and

a support for supporting the reflecting mirror.

[47]

A solar thermal power generation system comprising

the reflector device according to item [46], and

an apparatus for converting sunlight collected by the reflector deviceinto electric energy.

Advantageous Effects of Invention

According to the present invention, it is possible to provide a coatingcomposition for forming a coating film excellent in antifoulingproperties, transparency and hydrophilicity and capable of maintainingsurface hydrophilicity even at high temperature.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic sectional view of a laminate according to anembodiment of the present invention.

FIG. 2 is a schematic sectional view of a solar cell module according toan embodiment of the present invention.

FIG. 3 is a schematic perspective view of a reflector device accordingto an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

Embodiments for carrying out the present invention (hereinafter, simplyreferred to as the “embodiment(s)”) will be more specifically described.The embodiments below are merely illustration for explaining the presentinvention. The present invention would not be limited to the contentbelow. The present invention can be carried out by appropriatelymodifying it within the gist thereof.

In the specification, “(meth)acryl” refers to “acryl” and thecorresponding “methacryl”; “(meth)acrylate” refers to “acrylate” and thecorresponding “methacrylate”; and “(meth) acryloyl” refers to “acryloyl”and the corresponding “methacryloyl”.

<Coating Composition>

The coating composition of the embodiment contains

(A) a metal oxide particle having a number average particle size of 1 nmto 400 nm, and

(B) a polymer particle,

in which the content of an aqueous-phase component in the component (B),represented by the following expression (I), is 20 mass % or less.

The content of the aqueous-phase component (%)=(dry mass of a filtrateobtained by filtering the component (B) at a molecular cutoff of50,000)×(100−total mass of solid content)/(mass of the filtrate−dry massof the filtrate)×100/the total mass of solid content  (I).

The present inventors found out that the contact angle of the surface ofa coating film obtained increases mainly because an aqueous-phasecomponent (hydrophobic component) flows out from the coating film. Basedon the finding, they found that the hydrophilicity of the coating-filmsurface can be maintained by defining the content of the aqueous-phasecomponent in the component (B) so as to fall within the above range,thereby defining a distribution coefficient in an aqueous medium. Notethat the “coating film” described in the embodiment is not necessary tobe a continuous film and may be a form such as a discontinuous film, adispersed film like islands and the like.

Furthermore, it is preferable that the surface contact angle of the filmformed from an aqueous-phase component at 20° C. is 30° C. or less. Ifthe surface-water contact angle of the film formed from an aqueous-phasecomponent at 20° C. is larger than 30°, the content thereof ispreferably 5 mass % or less. The surface contact angle herein, whichrefers to the angle between a dry film and a tangent line of a waterdrop present on its surface, can be measured by a drop method. Note that“hydrophilicity” used in the embodiment means that the contact angle ofwater (23° C.) with respect to the surface of the object to be measuredis preferably 60° or less, more preferably 30° or less and furtherpreferably 20° or less.

Next, components that can be blended with a coating composition and acoating film will be described below.

The coating composition of the embodiment contains the component (A): ametal oxide having a number average particle size of 1 nm to 400 nm. Bythe presence of the component, the coating film having high transparencyand hydrophilicity can be obtained. The component (A) is thought tointeract with the component (B) and act as a curing agent for thecomponent (B) (however, the function is not limited to this). Examplesof the interaction may include, but not particularly limited to, ahydrogen bonding between a functional group (e.g., a hydroxy group andthe like) that the component (A) generally has and a functional group(e.g., a hydroxy group, a carboxyl group, an amide group, an aminogroup, an ether group and the like) that the component (B) has, achemical bonding (e.g., condensation) between the functional group thatthe component (A) generally has and the component (B) and the like.

The particle size of the component (A), which refers to a number averageparticle size (that may be a mixture of a primary particle and asecondary particle or either one of a primary particle and a secondaryparticle), is 1 nm to 400 nm, preferably 1 nm to 100 nm, more preferably3 nm to 80 nm and further preferably 5 nm to 50 nm. The number averageparticle size of the component (A) within the aforementioned range cancontribute to the optical characteristics and the like of the resultantcoating film, laminate and the like. Particularly, by adjusting thenumber average particle size to 100 nm or less, the light transmittanceof the resultant coating film and laminate can be greatly improved. Notethat the number average particle size of the embodiment (hereinafter,sometimes simply referred to as the “particle size”) is measured inaccordance with the method described in Examples (described later).

The metal oxide to be used in the component (A) is not particularlylimited, and a known metal oxide can be used. In view of the interactionwith the component (B), at least one oxide selected from the groupconsisting of silicon dioxide, aluminum oxide, antimony oxide, titaniumoxide, indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide,calcium silicate, magnesium oxide, niobium oxide and cerium oxide ispreferable. Of these, since a large number of surface hydroxy groups arepresent and interaction with the component (B) is particularly strong,at least one oxide selected from the group consisting of a silicondioxide (silica), aluminum oxide (alumina), antimony oxide and complexoxide of these is more preferable. Since, in forming a coating film asdescribed later, a continuous phase can be formed of the component (A)having a large number of surface hydroxy groups, with the result thatthe density of the hydroxy groups in the coating-film surface increasesand hydrophilicity thereof increases, the aforementioned metal oxidesare more preferable. The metal oxides of the component (A) may be usedsingly or in combinations of two or more.

Examples of the form of the component (A) include, but not particularlylimited to, powder, fluid dispersion, sol and the like. The “fluiddispersion” and “sol” refer to the state where the component (A) isdispersed in water, a hydrophilic organic solvent or a solvent mixtureof these in the form of at least one of a primary particle and asecondary particle with a concentration of 0.01 to 80 mass % andpreferably 0.1 to 50 mass %.

Examples of the hydrophilic organic solvent include alcohols such asethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol,ethanol, methanol and the like; ketones such as acetone, methyl ethylketone, methyl isobutyl ketone and the like; ethers such astetrahydrofuran, dioxane and the like; amides such as dimethylacetamide,dimethylformamide and the like; dimethyl sulfoxide; nitrobenzene; and amixture of two or more thereof.

Depending upon the properties to be added to a coating composition or acoating film, a preferable component can be appropriately selected asthe component (A) from the aforementioned components and othercomponents. Examples of the properties to be added to a coatingcomposition or a coating film include antireflection properties, solventresistance, antistatic properties, heat resistance, hard coatingproperties, photocatalyst activity and the like. Depending upon desiredproperties, the component to be added, the content and number averageparticle size can be appropriately selected. Furthermore, in the caseswhere an effect of a specific performance is desirably enhanced, andwhere a plurality of performances are desirably added to the coatingcomposition, at least two types of metal oxides can be used incombination. Based on this viewpoint, typical compounds include (A1)silica, (A2) an infrared absorbent, (A3) a photocatalyst, (A4) aconductive metal oxide and the like. Now, these compounds will bedescribed below.

The component (A1) is not particularly limited as long as it is silica(so called “silicon dioxide”). A production process thereof is notparticularly limited. For example, production may be made by aprecipitation method, a dry method and the like. In view of handling,colloidal silica is more preferable. In the case where the component(A1) is colloidal silica, a sol-gel process can be used for preparationand a commercially available product can be used. In the case wherecolloidal silica is prepared by a sol-gel process, reference can be madeto Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968),Rickey D. Badley et al; Lang muir 6, 792-801 (1990); Journal of theJapan Society of Colour Material, 61[9] 488-493 (1988) and the like toprepare it.

Colloidal silica is a dispersion of silica, which contains silicondioxide as a fundamental unit, in water or a water soluble solvent. Thenumber average particle size thereof is preferably 1 nm to 400 nm, morepreferably 1 nm to 200 nm, further preferably 1 nm to 100 nm, andfurther more preferably 5 nm to 30 nm. By adjusting the number averageparticle size to 1 nm or more, the storage stability of the coating filmand the coating composition (described later) becomes more excellent. Byadjusting the number average particle size to 100 nm or less, thetransparency of the coating film is more improved. Colloidal silicahaving a particle size within the aforementioned range can be used inthe state of an aqueous fluid dispersion regardless of whether it isacidic or basic. The pH thereof can be appropriately selected dependingupon the stable region of the aqueous dispersion of the component (B)mixed in combination.

Examples of the acidic colloidal silica using water as a dispersionmedium include commercially available products such as SNOWTEX (trademark)-O, SNOWTEX-OS and SNOWTEX-OL manufactured by Nissan ChemicalIndustries, Ltd.; Adelite (trade mark) AT-20Q manufactured by ADEKACORPORATION; and Crebosol (trade mark) 20H12 and Crebosol 30CAL25,manufactured by Clariant (Japan) K.K.

Examples of the basic colloidal silica include silica stabilized withthe addition of an alkaline metal ion, an ammonium ion, an amine or thelike. More specifically, examples thereof include commercially availableproducts such as SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, SNOWTEX-C30,SNOWTEX-CM40, SNOWTEX-N, SNOWTEX-N30, SNOWTEX-K, SNOWTEX-XL, SNOWTEX-YL,SNOWTEX-ZL, SNOWTEX PS-M and SNOWTEX PS-L manufactured by NissanChemical Industries, Ltd.; Adelite AT-20, Adelite AT-30, Adelite AT-20N,Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40 andAdelite AT-50 manufactured by ADEKA CORPORATION; Crebosol 30R9, Crebosol30R50 and Crebosol 50R50 manufactured by Clariant (Japan) K.K.; andLedoux (trade mark) HS-40, Ledoux HS-30, Ledoux LS and Ledoux SM-30manufactured by Du Pont Kabushiki Kaisha.

Examples of the colloidal silica using a water soluble solvent as adispersion medium include commercially available products such asMA-ST-M (a number average particle size of 20 nm to 25 nm, dispersed inmethanol), IPA-ST (a number average particle size of 10 nm to 15 nm,dispersed in isopropyl alcohol), EG-ST (a number average particle sizeof 10 nm to 15 nm, dispersed in ethylene glycol), EG-ST-ZL (a numberaverage particle size of 70 nm to 100 nm, dispersed in ethylene glycol),NPC-ST (a number average particle size of 10 nm to 15 nm, dispersed inethylene glycol monopropyl ether) manufactured by Nissan ChemicalIndustries, Ltd.

The colloidal silica may be used singly or in combinations of two ormore. If the metal oxide serving as the component (A) contains colloidalsilica as a major component, alumina, sodium aluminate and the like maybe contained as a minor component. Furthermore, the colloidal silica mayexist together with a stabilizer such as an inorganic base (sodiumhydroxide, potassium hydroxide, lithium hydroxide, ammonia and the like)and an organic base (tetramethylammonium and the like). The maincomponent herein refers to a component contained in an amount of 50 mass% or more and preferably 70 mass % or more in the metal oxide.

The infrared absorbent serving as the component (A2), which has anabsorption band in the infrared region (wavelength 800 nm or more) is anorganic substance, an inorganic substance and a mixture thereof.Examples of the infrared absorbent include inorganic microparticles andorganic microparticles. Specific examples of the inorganicmicroparticles include microparticles of cerium oxide or zinc oxideoptionally coated with silica; transparent conductive microparticlessuch as indium oxide doped with tin (ITO), tin oxide doped with antimony(ATO) and tin oxide doped with fluorine (FTO); microparticles of a noblemetal such as silver, gold, platinum, rhodium and palladium, andcomposite tungsten-oxides represented by the formula MxWyOz (where, Mrepresents at least one element selected from the group consisting of H,He, an alkali metal, an alkaline-earth metal, a rare-earth element, Mg,Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga,In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta,Re, Be, Hf, Os, Bi and I; W represents tungsten; and O representsoxygen, 0.0001≦x/y≦1.5, 1.0≦z/y≦5.0). Besides these, microparticleshaving absorption within the ultraviolet region, such as zirconiumoxide, tin oxide, bismuth oxide and titanium oxide may be used singly orin combinations of two or more.

These infrared absorbents are relatively stable and can bemicroparticulated and thus are preferable since they can absorb light inthe infrared wavelength region while suppressing scattering in a visiblelight region. Of these, at least one selected from the group consistingof the infrared absorbent coated with ITO, ATO, cerium oxide, zinc oxideor silica is more preferable.

The organic microparticle is not particularly limited in type andcomposition as long as it is a pigment having a maximum absorptionwavelength within a near-infrared light (800 nm to 1100 nm) wavelengthregion and the like. For example, a diimonium-based near-infrared lightabsorption pigment is preferable. The diimonium-based near-infraredlight absorption pigment has a strong absorbance of about 100,000 ofmolar absorption coefficient in the near-infrared light region of awavelength of 850 nm to 1100 nm and a weak absorbance in the visiblelight region of 400 nm to 500 nm in wavelength. Therefore, thetransmitted light is yellow-brown. However, since visible-lighttransmittance of the pigment is superior to other near-infrared lightabsorbing pigments, the diimonium-based near-infrared light absorptionpigment is preferable in order to obtain a high transmittance within thevisible light range. One or more pigments selected from the groupconsisting of a phthalocyanine pigment, an organic metal complex pigmentand a cyanine pigment, which have a maximum absorption in a wavelengthof 750 nm to 950 nm and no absorption within a visible light range, maybe used singly or in combinations of two or more. Furthermore, aconductive polymer represented by polyaniline, polypyrrol,polythiophene, polyvinyl sulfonic acid and the like can be used.

In order to provide a coating film with thermal insulating properties,coloring pigments can be used as the component (A2) singly or incombination. In this case, the coloring pigment preferably has a solarreflectance, for example defined in JIS A5759-1998, of 13% or more.Specific examples thereof include white pigments such as titanium whiteand a zinc oxide pigment; red pigments such as an iron oxide pigment anda quinacridon pigment; yellow pigments such as an iron oxide pigment, aniron hydroxide pigment, a lead chromate pigment and an azo pigment; bluepigments such as phthalocyanine blue and a complex oxide pigment; andgreen pigments such as chromium green and phthalocyanine green pigment.

An infrared absorbent ideally has no absorption in the infraredwavelength region of sunlight, particularly, a wavelength regioncorresponding to a silicon absorption band, and preferably has anaverage reflectivity of 25% or less within a visible ultraviolet lightregion of 300 nm to 780 nm in wavelength and an average reflectivity of15% or more within an infrared light region of 780 nm to 2500 nm inwavelength.

In the case where the component (A2) is contained, an absorbance of 0.1%or more is preferably obtained in the wavelength region of 1000 nm to2500 nm. In the wavelength region of 1000 nm to 2500 nm, where infraredlight can be efficiently converted into heat, the absorbance ispreferably 0.1% or more, and more preferably 10% or more. However, sincethe wavelength region overlaps with a silicon absorption region, theaddition amount can be controlled depending upon the absorption capacityof an infrared absorbent.

The particle size is controlled so as not to scatter light within thesilicon absorption wavelength range by scattering of particles. In thismanner, an increase of temperature can be effectively suppressed withoutaffecting the performance of solar cell power generation. In view ofthis, the number average particle size is preferably 10 nm to 2000 nm,more preferably 10 nm to 1500 nm and further preferably 10 nm to 1000nm. The number average particle size of 10 nm or more enables dispersionstability to be maintained. The number average particle size of 2000 nmor less suppresses increase of the intensity of scattered light andreduction of the power generation efficiency of a solar cell, even ifthe addition amount of component (A2) is large.

Generally, since these infrared absorbents tend to be less dispersed inan aqueous solvent, an infrared absorbent (A2) whose surface isuniformly or nonuniformly coated with silica used as the component (A1)is preferable. This enables the blending stability with the component(A1), the weather-resistance of the infrared absorbent (A2) and the liketo be further improved. A method for coating the infrared absorbent (A2)with silica (A1) is not particularly limited and a known method isemployed. For example, the infrared absorbent is dispersed in water andsubjected to a dispersion treatment performed by a high-pressurehomogenizer, and thereafter tetraethoxy silane, water glass and the likeare added thereto with stirring and while appropriately controlling pHsimultaneously controlling temperature to obtain an infrared absorbentcoated with silica.

Examples of the form of the component (A2) include, but not particularlylimited to, powder, fluid dispersion, sol and the like. The “fluiddispersion” and “sol” herein refer to a state where the component (A2)is dispersed in water and/or a hydrophilic organic solvent in aconcentration of 0.01 to 80 mass % and preferably 0.1 to 50 mass % inthe form of a primary particle and/or secondary particle.

The number average particle size of the component (A2) observed in thefluid dispersion or sol can contribute to optical characteristics of theresultant coating film and the like. Particularly, if the number averageparticle size is 100 nm or less, the transparency of the resultantcoating film can be significantly improved.

The photocatalyst serving as the component (A3) refers to a compound(hereinafter, sometimes simply referred to as the “photocatalyst”)exhibiting at least one of photocatalyst activity and hydrophilicity bylight irradiation. If a compound exhibits photocatalyst activity bylight irradiation, the surface of the resultant coating film isexcellent in activity (organic substance degradability) of decomposing acontaminant organic substance and resistance to fouling.

Examples of the photocatalyst include TiO₂, ZnO, SrTiO₃, BaTiO₃, BaTiO₄,BaTi₄O₉, K₂NbO₃, Nb₂O₅, Fe₂O₃, Ta₂O₅, K₃Ta₃Si₂O₃, WO₃, SnO₂, Bi₂O₃,BiVO₄, NiO, Cu₂O, RuO₂, CeO₂, and further, a sheet oxide having at leastone element selected from the group consisting of Ti, Nb, Ta and V (see,for example, Japanese Patent Application Laid-Open No. 62-74452,Japanese Patent Application Laid-Open No. 2-172535, Japanese PatentApplication Laid-Open No. 7-24329, Japanese Patent Application Laid-OpenNo. 8-89799, Japanese Patent Application Laid-Open No. 8-89800, JapanesePatent Application Laid-Open No. 8-89804, Japanese Patent ApplicationLaid-Open No. 8-198061, Japanese Patent Application Laid-Open No.9-248465, Japanese Patent Application Laid-Open No. 10-99694 andJapanese Patent Application Laid-Open No. 10-244165). Of thesephotocatalysts, TiO₂ (titanium oxide) is preferable since it is nontoxicand excellent in chemical stability. The titanium oxide with an anatasestructure, a rutile structure or a brookite structure can be used.

In view of exhibiting antistatic properties of the resultant coatingcomposition and the like, a conductive metal oxide can be used as thecomponent (A4). Examples of such a conductive metal oxide include indiumoxide (ITO) doped with tin, tin oxide (ATO) doped with antimony, tinoxide, zinc oxide and the like. Furthermore, in view of the interactionwith the component (B), for example, aluminum oxide, antimony oxide,indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide,calcium silicate, magnesium oxide, niobium oxide and cerium oxide, canbe used in combination with the conductive metal oxide.

The component (B) is a polymer particle. In the coating film of theembodiment, it is preferable that (B) the polymer particle is surroundedby the component (A). (B) The polymer particle refers to a polymerparticle obtained by polymerizing a monomer component having anunsaturated bond in the presence of a radical, a cation and/or an anion.

In the embodiment, the content of the aqueous-phase component of thecomponent (B), represented by the expression (I) is 20 mass % or less.By adjusting the content of the aqueous-phase component of the component(B) to 20 mass % or less, transparency and hydrophilicity becomeexcellent and excellent hydrophilicity can be maintained even at hightemperature.

The content of the aqueous-phase component (%)=(dry mass of a filtrateobtained by filtering the component (B) at a molecular cutoff of50,000)×(100−total mass of solid content)/(mass of the filtrate−dry massof the filtrate)×100/the total mass of solid content  (I).

The content of the aqueous-phase component of the component (B) ispreferably 15 mass % or less and more preferably 10 mass % or less,thereby having excellent antifouling properties, transparency andhydrophilicity, and maintaining excellent hydrophilicity not only athigh temperature but also at high humidity as well as even at hightemperature/humidity.

The component (B) is preferably an emulsion particle. By virtue of theemulsion particle, a sea-island structure can be formed by the component(A) and the component (B) when a coating film (described later) isformed. By forming the sea-island structure, a metal oxide is localizedin the uppermost surface of the coating film and thus hydrophilicity canbe satisfactorily exhibited by a hydrophilic group such as a hydroxygroup of the metal oxide. Examples of the emulsion particle include, butnot particularly limited to, an acryl emulsion, a styrene emulsion, anacrylstyrene emulsion, an acryl silicon emulsion, a silicon emulsion anda fluorine resin emulsion.

The component (B) is more preferably a polymer emulsion particleobtained, in a polymerization material solution containing a component(b1): a hydrolyzable silicon compound, a component (b2): a vinylmonomer, a component (b3): an emulsifier and a component (b4): water, bypolymerizing the component (b1) and the component (b2). The component(B) thus obtained and that can be preferably used is a compound obtainedby conjugating a hydroxy group derived from the component (b1) and apolymerization product serving as the component (b2) via a hydrogen bondand the like.

Examples of the component (b1) include a compound represented by thefollowing formula (4) and a condensate thereof, and a silane couplingagent.

SiW_(x)R_(y)  (4)

where W represents at least one group selected from the group consistingof an alkoxy group having 1 to 20 carbon atoms, a hydroxy group, anacetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogenatom, an oxime group having 1 to 20 carbon atoms, an enoxy group, anaminoxy group and an amide group; R represents at least one hydrocarbongroup selected from the group consisting of a linear or branched alkylgroup having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20carbon atoms and an aryl group having 6 to 20 carbon atoms unsubstitutedor substituted with an alkyl group having 1 to 20 carbon atoms, analkoxy group having 1 to 20 carbon atoms or a halogen atom; x is aninteger of 1 or more and 4 or less, y is an integer of 0 or more and 3or less; and x+y=4.

The silane coupling agent refers to a silane derivative havingintramolecular functional group which is reactive with an organicsubstance such as a vinyl polymerizable group, an epoxy group, an aminogroup, a methacryl group, a mercapto group and an isocyanate group.

Specific examples of the compound represented by the formula (4) includetetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane,tetra-n-propoxysilane, tetraisopropoxysilane and tetra-n-butoxysilane;trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, isopropyltrimethoxysilane,isopropyltriethoxysilane, n-butyltrimethoxysilane,n-butyltriethoxysilane, n-pentyltrimethoxysilane,n-hexyltrimethoxysilane, n-heptyltrimethoxysilane,n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,allyltrimethoxysilane, cyclohexyltrimethoxysilane,cyclohexyltriethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, 3-chloropropyltrimethoxysilane,3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane,2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane,2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane,3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane,3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane,3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth) acryloxypropyltriethoxysilane,3-(meth) acryloyloxypropyltri-n-propoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysilane and3-ureidopropyltriethoxysilane; dialkoxysilanes such asdimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,diethyldiethoxysilane, di-n-propyldimethoxysilane,di-n-propyldiethoxysilane, diisopropyldimethoxysilane,diisopropyldiethoxysilane, di-n-butyldimethoxysilane,di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane,di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane,di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane,di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane,di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane,di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane and 3-(meth)acryloyloxypropylmethyldimethoxysilane; and monoalkoxysilanes such astrimethylmethoxysilane and trimethylethoxysilane. These may be usedsingly or in combinations of two or more.

As the component (b1), a silicon alkoxide having a phenyl group (forexample, phenyltrimethoxysilane, phenyltriethoxysilane anddiphenyldimethoxysilane) can be used. A silicon alkoxide having a phenylgroup is preferably used because polymerization stability in thepresence of water and an emulsifier becomes excellent.

The component (b1) may include a silane coupling agent having a thiolgroup and a component (b1-1): a hydrolyzable silicon compound having avinyl polymerizable group. These are preferably used as the component(b1) because the long-term antifouling properties of the resultantcoating film become excellent.

Examples of the silane coupling agent having a thiol group include3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

Examples of the component (b1-1) include a silane coupling agent havinga vinyl polymerizable group such as3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltri-n-propoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, allyltrimethoxysilane and 2-trimethoxysilylethylvinyl ether.

These silane coupling agents can produce a chemical bond viacopolymerization or chain transfer reaction with component (b2)(described later). Therefore, if a silane coupling agent having a vinylpolymerizable group or a thiol group is mixed or conjugated with theaforementioned component (b1), a polymerization product of the component(b1) and a polymerization product of the component (b2) (describedlater) can be conjugated by a chemical bond.

In the component (b1-1), examples of the “vinyl polymerizable group”include a vinyl group and an allyl group. Of these,3-(meth)acryloxypropyl group is preferable.

The component (b1) may include a component (b1-2): a cyclic siloxaneoligomer. Use of the component (b1-2) is preferable because theflexibility of the resultant coating film is more improved.

Examples of the cyclic siloxane oligomer may include compoundsrepresented by the following formula (5).

(R′₂SiO)_(m)  (5)

where R′ is at least one selected from the group consisting of ahydrogen atom, a linear or branched alkyl group having 1 to 30 carbonatoms, a cycloalkyl group having 5 to 20 carbon atoms and an aryl grouphaving 6 to 20 carbon atoms unsubstituted or substituted with an alkylgroup having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbonatoms or a halogen atom; m is an integer; and 2≦m≦20.

Of them, in view of reactivity and the like, a cyclic dimethylsiloxaneoligomer such as octamethylcyclotetrasiloxane is preferable.

If a condensate is used as the component (b1), thepolystyrene-equivalent weight average molecular weight (by the GPCmethod) of the condensate is preferably 200 to 5000 and more preferably300 to 1000.

The mass ratio ((b1)/(B)) of the content of the component (b1) to thecontent of the component (B) is preferably 0.01/100 to 80/100 and morepreferably 0.1/100 to 70/100 in view of polymerization stability.

The mass ratio ((b1-1)/(B)) of the content of the component (b1-1) tothe content of the component (B) is preferably 0.01/100 to 20/100 andmore preferably 0.5/100 to 10/100 in view of polymerization stability.The mass ratio ((b1-1)/(b2)) of the content of the component (b1-1) tothe content of the component (b2) is preferably 0.1/100 to 100/100 andmore preferably 0.5/100 to 50/100 in view of polymerization stability.

The mass ratio ((b1-2)/(B)) of the content of the component (b1-2) tothe content of the component (B) is preferably 0.01/100 to 20/100 andmore preferably 0.5/100 to 5/100 in view of hydrophilicity. The massratio ((b1-2)/(b2)) of the content of the component (b1-2) to thecontent of the component (b2) is preferably 0.5/100 to 50/100 and morepreferably 1.0/100 to 20/100 in view of polymerization stability.

The component (b2) is a vinyl monomer. The component (b2) is preferablya vinyl monomer having at least one functional group selected from thegroup consisting of a hydroxy group, a carboxyl group, an amide group,an amino group and an ether group. If the vinyl monomer has such afunctional group, chemical bonding (for example, condensation) to afunctional group of a component other than the component (B) (forexample, a metal oxide of the component (A)) can be easily made,enhancing interaction.

Specific examples of the hydroxy group-containing vinyl monomer servingas the component (b2) include a hydroxyalkyl(meth)acrylate such as2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate or4-hydroxybutyl(meth)acrylate; a hydroxy group-containing vinyl ethersuch as 2-hydroxyethylvinyl ether or 4-hydroxybutylvinyl ether; ahydroxy group-containing allyl ether such as 2-hydroxyethyl allyl ether;a monoester of a polyoxyalkylene glycol obtained from a polyether polyolrepresented by polyethylene glycol and an unsaturated carboxylic acidrepresented by (meth)acrylic acid; an adduct of any one of the hydroxygroup-containing monomers mentioned above and a lactone represented byc-caprolactone; an adduct of an epoxy group-containing unsaturatedmonomer represented by glycidyl(meth)acrylate and an acid represented byacetic acid; and an adduct of an unsaturated carboxylic acid representedby (meth)acryl acid and a monoepoxy compound except for α-olefin epoxiderepresented by “Cardura-E” (trade name, manufactured by Shell inNetherland).

Specific examples of the carboxyl group-containing vinyl monomermentioned as the component (b2) include an unsaturated carboxylic acidsuch as (meth)acrylic acid, 2-carboxyethyl(meth)acrylate, crotonic acid,itaconic acid, maleic acid or fumaric acid; a monoester (half ester) ofan unsaturated dicarboxylic acid and a saturated monoalcohol such asmonomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate,mono-n-butyl maleate, monomethyl fumalate, mono-n-butyl fumalate; amonovinyl ester of a saturated dicarboxylic acid such as monovinyladipate or monovinyl succinate; a product of an addition reactionbetween a saturated polycarboxylic acid anhydride such as a succinicanhydride, a glutaric anhydride, a phthalic anhydrite or trimelliticanhydride, and any one of the hydroxy group-containing vinyl monomersmentioned above; and a monomer obtained by an addition reaction of anyone of the carboxyl group-containing monomer mentioned above and alactone.

Specific examples of the amino group-containing vinyl monomer mentionedas the component (b2) include a tertiary amino group-containing(meth)acrylate such as 2-dimethylaminoethyl(meth)acrylate,2-diethylaminoethyl(meth)acrylate,2-di-n-propylaminoethyl(meth)acrylate,3-dimethylaminopropyl(meth)acrylate, 4-dimethylaminobutyl(meth)acrylateor N-[2-(meth)acryloyloxy]ethyl morpholine; a tertiary aminogroup-containing aromatic vinyl monomer such as vinylpyridine,N-vinylcarbazole or N-vinylquinoline; a tertiary amino group-containing(meth)acrylamide such as N-(2-dimethylamino)ethyl(meth)acrylamide,N-(2-diethylamino)ethyl(meth)acrylamide,N-(2-di-n-propylamino)ethyl(meth)acrylamide,N-(3-dimethylamino)propyl(meth)acrylamide,N-(4-dimethylamino)butyl(meth)acrylamide orN-[2-(meth)acrylamide]ethylmorpholine; a tertiary amino group-containingcrotonic acid amide such as N-(2-dimethylamino)ethylcrotonic acid amide,N-(2-diethylamino)ethylcrotonic acid amide,N-(2-di-n-propylamino)ethylcrotonic acid amide,N-(3-dimethylamino)propylcrotonic acid amide orN-(4-dimethylamino)butylcrotonic acid amide; and a tertiary aminogroup-containing vinyl ether such as 2-dimethylaminoethyl vinyl ether,2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether or4-dimethylaminobutyl vinyl ether.

Specific examples of the ether group-containing vinyl monomer mentionedas the component (b2) include vinyl monomers such as a vinyl etherhaving a polyether chain in a side chain such as polyoxyethylenealkylether, polyoxyethylenealkylphenyl ether, a higher fatty acid ester of apolyoxyethylene or a polyoxyethylene-polyoxypropylene block copolymer;an allyl ether and a (meth)acrylate. As the ether group-containing vinylmonomer, a commercially available product can be used. Examples thereofinclude BLEMMER PE-90, PE-200, PE-350, PME-100, PME-200, PME-400 andAE-350 (trade name, manufactured by NOF Corporation); and MA-30, MA-50,MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114 andMPG130-MA (trade name, manufactured by Nippon Nyukazai Co., Ltd.). Thenumber of oxyethylene units of the polyoxyethylene chain herein ispreferably 2 to 30. If the number is less than 2, the flexibility of theresultant coating film tends to be insufficient. If the number exceeds30, the resultant coating film becomes flexible and thus tends to beinferior in blocking resistance.

Specific examples of the amide group-containing vinyl monomer mentionedas the component (b2) include N-alkyl- or N-alkylene-substituted(meth)acrylamide. More specific examples thereof includeN-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide,N,N-dimethylacrylamide, N,N-dimethylmethacrylamide,N,N-diethylacrylamide, N-ethylmethacrylamide,N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide,N-isopropylacrylamide, N-n-propylacrylamide, N-isopropylmethacrylamide,N-n-propylmethacrylamide, N-methyl-N-n-propylacrylamide,N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine,N-methacryloylpyrrolidine, N-acryloylpiperidine,N-methacryloylpiperidine, N-acryloylhexahydroazepine,N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone,N-vinylcaprolactam, N,N′-methylenebisacrylamide, N,N′-methylenebismethacrylamide, N-vinylacetamide, diacetoneacrylamide,diacetonemethacrylamide, N-methylolacrylamide andN-methylolmethacrylamide.

As the component (b2), in view of improving hydrogen bonding to othercomponents, a vinyl monomer containing a secondary amide group, atertiary amide group or both of them is preferable. Particularly, avinyl monomer having a tertiary amide group is preferable in view ofhydrogen bonding power.

The mass ratio ((b2)/(B)) of the content of the component (b2) to thecontent of the component (B) is 0.01/1 to 1/1 in view of polymerizationstability, preferably 0.1/1 to 0.5/1 and more preferably 0.2/1 to 0.4/1.

The mass ratio ((b2)/(A1)) of the content of the component (b2) to thecontent of the component (A1) is 0.01/1 to 1/1 in view of hydrogenbonding and blending stability, preferably 0.1/1 to 1/1 and morepreferably 0.2/1 to 0.7/1.

Examples of the component (b3) include an acidic emulsifier such asalkylbenzene sulfonic acid, alkyl sulfonic acid, alkylsulfosuccinicacid, polyoxyethylenealkyl sulfuric acid, polyoxyethylenealkylarylsulfuric acid and polyoxyethylene distyrylphenylether sulfonicacid; an anionic surfactant such as an alkaline metal (e.g., Li, Na, K)salt of an acidic emulsifier, an ammonium salt of an acidic emulsifierand fatty acid soap; cationic surfactant of a quaternary ammonium salt,a pyridinium salt and an imidazolinium salt such asalkyltrimethylammonium bromide, alkylpyridinium bromide andimidazolinium laurate; a nonionic surfactant such as polyoxyethylenealkylaryl ether, a polyoxyethylene sorbitan fatty acid ester, apolyoxyethylene oxypropylene block copolymer and polyoxyethylenedistyryl phenyl ether, and the like. These may be used singly or incombinations of two or more.

As the component (b3), in view of improving water dispersion stabilityof the resultant component (B) and improving long-term antifoulingproperties of the resultant coating film, a reactive emulsifier having aradical polymerizable double bond is preferably used. Examples of thereactive emulsifier include a vinyl monomer having a sulfonic acid groupor a sulfonate group, a vinyl monomer having a sulfuric acid ester groupand an alkali metal salt and ammonium salt thereof; a vinyl monomerhaving a nonionic group such as polyoxyethylene and a vinyl monomerhaving a quaternary ammonium salt.

Examples of the vinyl monomer having a sulfonic acid group or asulfonate group include a compound having a radical polymerizable doublebond and having a substituent selected from the group consisting of analkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, aphenyl group, a naphthyl group and a succinic acid group, which arepartly substituted with a substituent such as an ammonium salt, sodiumsalt or potassium salt of a sulfonic acid group; and a vinyl sulfonatecompound having a vinyl group to which a substituent such as an ammoniumsalt, a sodium salt or a potassium salt of a sulfonic acid group isbound.

Examples of the vinyl monomer having a sulfuric acid ester group includea compound having a radical polymerizable double bond and a substituentselected from the group consisting of an alkyl group having 1 to 20carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, apolyalkyl ether group having 2 to 4 carbon atoms, a phenyl group and anaphthyl group, which are partly substituted with a substituent such asan ammonium salt, sodium salt or potassium salt of a sulfonic acid estergroup.

Specific examples of the compound having a succinic acid group partlysubstituted with a substituent such as an ammonium salt, sodium salt orpotassium salt of a sulfonic acid group include an allyl sulfosuccinate. More specific examples include ELEMINOL JS-2 (trade name,manufactured by Sanyo Chemical Industries, Ltd.) and Latemul S-120,S-180A or S-180 (trade name, manufactured by Kao Corp.).

Specific examples of the compound having an alkyl ether group having 2to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atomspartly substituted with a substituent such as an ammonium salt, sodiumsalt or potassium salt of a sulfonic acid group include Aqualon HS-10 orKH-1025 (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)and ADEKA REASOAP SE-1025N or SR-1025 (trade name, manufactured by ADEKACORPORATION).

Specific examples of the vinyl monomer having a nonion group includeα-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxypolyoxyethylene(trade name: e.g., ADEKA REASOAP NE-20, NE-30 and NE-40 manufactured byADEKA CORPORATION) and polyoxyethylene alkylpropenyl phenyl ether (tradename: e.g., Aqualon RN-10, RN-20, RN-30 and RN-50, Dai-ichi KogyoSeiyaku Co., Ltd.).

The use amount of component (b3) to 100 parts by mass of the component(B) is preferably 10 not more than parts by mass and more preferably0.001 to 5 parts by mass, in view of polymerization stability.

The component (B) is a polymer emulsion particle, which is obtained, ina polymerization material solution containing the aforementionedcomponents (b1) to (b3) and a component (b4) (i.e., water), bypolymerizing the component (b1) and the component (b2). The use amountof component (b4), i.e., the content thereof in the polymerizationmaterial solution, is preferably 30 to 99.9 mass %, in view ofpolymerization stability.

To the polymerization material solution, in addition to the components(b1) to (b4), various components can be further added. First, to thepolymerization material solution, it is preferable that the component(b5): another vinyl monomer copolymerizable with the component (b2), canbe further added. Use of such a component (b5) is preferable to controlproperties of the polymerization product to be produced (glasstransition temperature, molecular weight, hydrogen bonding ability,polar, dispersion stability, weather-resistance, compatibility with apolymerization product of hydrolyzable silicon compound serving as thecomponent (b1) and the like).

Examples of the component (b5) include an acrylate, a methacrylate, anaromatic vinyl compound and a vinyl cyanide. Other than these, examplesthereof include a functional group-containing monomer such as an epoxygroup-containing vinyl monomer, a carbonyl group-containing vinylmonomer and an anionic vinyl monomer.

The ratio of the component (b5) in the total vinyl monomer preferablyfalls within the range of 0.001 to 30 mass % and more preferably 0.05 to10 mass %. Use of the component (b5) within this range is preferablesince glass transition temperature, molecular weight, hydrogen bondingability, polarity, dispersion stability, weather-resistance,compatibility with a polymerization product of a hydrolyzable siliconcompound serving as the component (b1) and the like can be controlled.

To the polymerization material solution, a chain transfer agent can beadded. Examples of the chain transfer agent include an alkyl mercaptansuch as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan;an aromatic mercaptan such as benzyl mercaptan and dodecyl benzylmercaptan; and a thiocarboxylic acid such as thiomalic acid, a saltthereof or an alkyl ester thereof, or a polythiole, diisopropylxanthogen disulfide, di(methylenetrimethylolpropane) xanthogendisulfide, thioglycol and an allyl compound such as a dimer ofα-methylstyrene.

The use amount of chain transfer agents to the total vinyl monomer (100parts by mass) is preferably 0.001 to 30 parts by mass and morepreferably 0.05 to 10 parts by mass. Use of a chain transfer agentwithin the range is preferable in view of polymerization stability.

Furthermore, in the polymerization material solution, a dispersionstabilizer can be blended. Examples of the dispersion stabilizerinclude, but not particularly limited to, a water soluble oligomerselected from the group consisting of a polycarboxylic acid and asulfonate and a synthetic or naturally occurring water soluble or waterdispersible polymer substance such as polyvinyl alcohol,hydroxyethylcellulose, starch, maleinized polybutadiene, maleinizedalkyd resin, polyacrylic acid (polyacrylate), polyacrylamide, and awater soluble or water dispersible acrylic resin. These may be usedsingly or in combinations of two or more.

The use amount of dispersion stabilizer to 100 parts by mass of thecomponent (B), i.e., a polymer emulsion particle, is preferably not morethan 10 parts by mass and more preferably 0.001 to 5 parts by mass.

Polymerization of the aforementioned polymerization material solution ispreferably performed in the presence of a polymerization catalyst.Example of the polymerization catalyst serving as the component (b1)include an acidic compound such as a hydrogen halide such ashydrochloric acid and hydrofluoric acid, a carboxylic acid such asacetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid,a sulfonic acid such as sulfuric acid and p-toluene sulfonic acid, anacidic emulsifier such as alkylbenzenesulfonic acid, alkylsulfonic acid,alkylsulfosuccinic acid, polyoxyethylene alkyl sulfuric acid,polyoxyethylene alkylaryl sulfuric acid and polyoxyethylene distyrylphenyl ether sulfonic acid, acidic or weak acidic inorganic salt,phthalic acid, phosphoric acid and nitric acid; a basic compound such assodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate,tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylene diamine, diethylene triamine, anethanol amine, γ-aminopropyltrimethoxysilane andγ-(2-aminoethyl)-aminopropyltrimethoxysilane; and a tin compound such asdibutyltin octylate and dibutyltin dilaurate. Of these, a polymerizationcatalyst of a hydrolyzable silicon compound serving as the component(b1) is preferably an acidic emulsifier having a function of not only apolymerization catalyst but also an emulsifier, particularly, analkylbenzenesulfonic acid (dodecyl benzene sulfonic acid and the like)having 5 to 30 carbon atoms.

As the polymerization catalyst for the component (b2), a radicalpolymerization catalyst is preferable, which causes radicaldecomposition by heat or a reducible substance and the like and causesaddition polymerization of a vinyl monomer. Examples of such a radicalpolymerization catalyst preferably include a water soluble or oilsoluble persulfate, peroxide and azobis compound. More specific exampleof the radical polymerization catalyst include potassium persulfate,sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butylhydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile,2,2-azobis(2-diaminopropane) hydrochloride and2,2-azobis(2,4-dimethylvaleronitrile).

The use amount of polymerization catalyst to 100 parts by mass of thetotal vinyl monomer is preferably 0.001 to 5 parts by mass. If apolymerization rate is desired to increase and polymerization is desiredto perform at a temperature as low as 70° C. or less, it is advantageousif a reducing agent such as sodium bisulfite, ferrous chloride,ascorbate and Rongalite is used in combination with a radicalpolymerization catalyst.

In the embodiment, polymerization of the component (b1) andpolymerization of the component (b2) can be separately performed;however, they are preferably performed simultaneously because microorganic/inorganic conjugation can be attained by a hydrogen bond and thelike.

As a method for obtaining the component (B), so-called emulsionpolymerization is suitable in which the component (b1) and the component(b2) are polymerized in the presence of a sufficient amount of water forthe emulsifier to form a micelle. In an example of the emulsionpolymerization method, the component (b1) and the component (b2), ifnecessary, further the component (b3) are added dropwise directly or inan emulsion state, at one time, in lots or continuously, to a reactionvessel and polymerized in the presence of a polymerization catalyst, ata pressure of preferably atmospheric pressure to 10 MPa, if necessary ata reaction temperature of about 30 to 150° C. However, polymerizationmay be performed, if necessary, at the aforementioned pressure or moreor the aforementioned temperature or less.

The polymerization material solution is preferably prepared, in view ofpolymerization stability, by blending components (b1) to (b4) such thatthe total mass of the solid contents falls within the range of 0.1 to 70mass % and preferably 1 to 55 mass %. The total mass (mass %) of thesolid contents is obtained by placing and drying the component (B) in anoven heated to 100° C. for 2 hours to obtain the dry weight of the solidcontents, and calculating in accordance with the following expression(II).

Total mass of solid contents (mass %)=dry mass/mass of component(B)×100  (II)

In carrying out the emulsion polymerization, in view of appropriatelygrowing the particle or controlling the particle size of the resultantcomponent (B), a seed polymerization method is preferably employed. Inthe seed polymerization method, an emulsion particle (seed particle) ispreviously placed in an aqueous phase and then polymerization isperformed. The pH of the polymerization system when a seedpolymerization method is carried out is preferably 1.0 to 10.0 and morepreferably 1.0 to 6.0. The pH can be adjusted by use of a pH buffer suchas disodium phosphate, borax, sodium hydrogen carbonate and ammonia.

As a method for obtaining the component (B), a method of polymerizingcomponent (b1) and component (b2) in the presence of component (b3) andcomponent (b4) required for polymerizing component (b1) and, ifnecessary, in the presence of a solvent, followed by adding water untila polymerization product is emulsified, can be applied.

The component (B) preferably has a core/shell structure having a corelayer and one or two or more shell layers covering the core layer inview of improving the adhesion of the resultant coating film to asubstrate. A method for forming the core/shell structure, multistageemulsion polymerization, in which emulsion polymerization is performedin multiple stages, is extremely useful. The core/shell structure can beobserved, for example, by a morphological observation by means of atransmission electron microscope and the like and analysis byviscoelastic measurement.

The component (B) is a polymer emulsion particle obtained bypolymerizing the component (b1) and the component (b2) in thepolymerization material solution containing a seed particle forming thecore layer. The seed particle is more preferably a particle obtained bypolymerizing the component (b1), the component (b2) and the component(b5): at least one component selected from the group consisting of othervinyl monomers copolymerizable with the component (b2). Also in thiscase, multistage emulsion polymerization is useful.

The multistage emulsion polymerization specifically consists of e.g., afirst stage of polymerizing, in the presence of the component (b3) andcomponent (b4), the component (b1), the component (b2) and at least onecomponent selected from the group consisting of the components (b5) toform a seed particle, and a second stage of polymerization is performed,in the presence of the seed particle, by adding a polymerizationmaterial solution containing the component (b1) and the component (b2),and, if necessary, the component (b5) (2-stage polymerization method).In the case where multistage emulsion polymerization consisting of threestages or more is performed, for example, polymerization of the thirdstage is performed by further adding a polymerization material solutioncontaining the component (b1) and the component (b2) and, if necessary,the component (b5). Such a method is preferable in view ofpolymerization stability.

In the case where the two-stage polymerization method is employed, massratio ((M1)/(M2)) of the solid content mass (M1) in the polymerizationmaterial solution used in the first stage to the solid content mass (M2)in the polymerization material solution to be added in the second stageis preferably 9/1 to 1/9 and more preferably 8/2 to 2/8 in view ofpolymerization stability.

Furthermore, as the core/shell structure, in view of polymerizationstability, it is preferable that a particle size is increased by thesecond-stage polymerization without significantly changing the sizedistribution (volume average particle size/number average particle size)of the seed particle. The volume average particle size can be measuredin the same manner as in the number average particle size.

In the polymer emulsion particle (B), a mass ratio ((b2)/(b1)) of thecontent of the component (b2) to the content of the component (b1) inthe core layer is preferably 0.01/1 to 1/1. In the outermost shelllayer, a mass ratio ((b2)/(b1)) of the content of the component (b2) tothe content of the component (b1) is preferably 0.01/1 to 5/1. In thecore layer, if the mass ratio ((b2)/(b1)) is 0.01/1 or more,polymerization stability tends to be more improved, whereas if the massratio is 1/1 or less, durability and flexibility are further improved.Furthermore, In the outermost shell layer, if the mass ratio ((b2)/(b1))is 0.01/1 or more, the interaction with the component (A) can beincreased, whereas if the mass ratio is 5/1 or less, the interaction canbe appropriately suppressed and sufficient stability tends to beobtained.

In the core/shell structure, the glass transition temperature (Tg) ofthe core layer is preferably 0° C. or less. This case is preferablesince the coating film having more excellent flexibility at roomtemperature can be obtained, with the result that a protective memberfor a solar cell rarely generating crack and the like can be produced.Tg can be measured by a differential scanning calorimeter (DSC) in theembodiment.

A number average particle size of the component (B) is preferably 10 nmto 800 nm. If the composition is formed by comprising the component (B)whose particle size is controlled to fall within the range, incombination with the component (A) having a number average particle sizeof 1 nm to 400 nm, weather resistance and antifouling properties arefurther improved. In view of improving the transparency of the resultantcoating film, a number average particle size of the component (B) ismore preferably 10 nm to 100 nm.

The ratio ((SA)/(SB)) of the surface area (SA) of the component (A) tothe surface area (SB) of the component (B) preferably falls within therange of 0.001 to 1000. The surface area of each component can becalculated based on particle sizes, mass values and specific gravityvalues of the component (A) and the component (B) and on the assumptionthat the shape of particles are true sphere.

In the embodiment, in addition to the aforementioned components,additional components usually added to a coating material and a moldingresin can be blended depending upon the application and the method to beemployed and the like. Examples thereof include a light stabilizer, a UVabsorbent, a thickening agent, a leveling agent, a thixotropy agent, adefoaming agent, a freezing stabilizer, a delustering agent, acrosslinking reaction catalyst, a pigment, a curing catalyst,crosslinking agent, a filler, an antiskinning agent, a dispersant, awetting agent, an antioxidant, a UV absorbent, a rheology controllingagent, a film-forming auxiliary, a rust preventing agent, a dye, aplasticizer, a lubricant, a reducing agent, an antiseptic agent, anantifungal agent, a deodorant, a yellowing inhibitor, an antistaticagent and a charge controller. They may be selected and used incombination depending upon the purpose.

As the light stabilizer, for example, hindered amine based lightstabilizers are preferably used. Of them, a radical polymerizable lightstabilizer having a radical polymerizable double bond within themolecule is preferable. As the UV absorbent, for example, an organic UVabsorbent can be mentioned. Examples of such an organic UV absorbentinclude a benzophenone UV absorbent, a benzotriazole UV absorbent and atriazine UV absorbent. Of these, a radical polymerizable UV absorbenthaving a radical polymerizable double bond within the molecule ispreferable. Furthermore, it is preferable to use a benzotriazole UVabsorbent and a triazine UV absorbent having a high UV ray absorptionability.

The light stabilizer is preferably used in combination with an organicUV absorbent. Use of them in combination possibly contributes to animprovement of weather-resistance of the resultant coating film.Furthermore, the organic UV absorbent, light stabilizer and additionalcomponents can be simply blended with the component (A1), component (A2)and component (B) and may be co-present in synthesizing the component(B).

The coating composition of the embodiment preferably further compriseshydrolyzable silicon compound as the component (C) for the purpose ofimproving the strength and antifouling properties of the resultantcoating film. As the hydrolyzable silicon-containing compound used asthe component (C), at least one selected from the group consisting of ahydrolyzable silicon-containing compound (c1) represented by thefollowing formula (1), a hydrolyzable silicon-containing compound (c2)represented by the following formula (2) and a hydrolyzable siliconcompound (c3) represented by the following formula (3) can be used.

R¹ _(n)SiX_(4-n)  (1)

where R¹ represents a hydrogen atom, or an alkyl group, alkenyl group,alkynyl group or aryl group having 1 to 10 carbon atoms and optionallyhaving a halogen group, a hydroxy group, a mercapto group, an aminogroup, a (meth)acryloyl group or an epoxy group; X represents ahydrolyzable group; and n is an integer of 0 to 3. The hydrolyzablegroup is not particularly limited as long as it hydrolytically producesa hydroxy group and examples thereof include a halogen atom, an alkoxygroup, an acyloxy group, an amino group, a phenoxy group and an oximegroup.

X₃Si—R² _(n)—SiX₃  (2)

where X represents a hydrolyzable group; R² represents an alkylene groupor phenylene group having 1 to 6 carbon atoms; and n is 0 or 1.

R³—(O—Si(OR³)₂)_(n)—OR³  (3)

where R³ represents an alkyl group having 1 to 6 carbon atoms; and n isan integer of 2 to 8.

Specific examples of the hydrolyzable silicon compounds (c1) and (c2)include tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane,tetra(1-propoxy)silane, tetra(n-butoxy)silane, tetra(1-butoxy)silane,tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane,triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane,propyltriethoxysilane, isobutyltriethoxysilane,cyclohexyltrimethoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, dimethoxysilane, diethoxysilane,methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, bis(trimethoxysilyl)methane,bis(triethoxysilyl)methane, bis(triphenoxysilyl)methane,bis(trimethoxysilyl)ethane, bis(triethoxysilyl)ethane,bis(triphenoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane,1,3-bis(triethoxysilyl)propane, 1,3-bis(triphenoxysilyl)propane,1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene,3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane, tetraacetoxysilane,tetrakis(trichloroacetoxy)silane, tetrakis(trifluoroacetoxy)silane,triacetoxysilane, tris(trichloroacetoxy)silane,tris(trifluoroacetoxy)silane, methyltriacetoxysilane,methyltris(trichloroacetoxy)silane, tetrachlorosilane, tetrabromosilane,tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane,methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane,tetrakis(methylethylketoxime)silane, tris(methylethylketoxime)silane,methyl tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilazane,hexamethylcyclotrisilazane, bis(dimethylamino)dimethylsilane,bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane andbis(diethylamino)methylsilane.

Specific examples of the hydrolyzable silicon compound (c3) representedby the above formula (3) include a partial hydrolytic condensate oftetramethoxysilane (for example, trade name “M silicate 51” manufacturedby Tama Chemicals Co., Ltd.; trade name “MSI51” manufactured by ColcoatCo., Ltd.; and trade name “MS51” and “MS56” manufactured by MitsubishiChemical Corporation), a partial hydrolytic condensate oftetraethoxysilane (trade name “Silicate 35” and “Silicate 45”manufactured by Tama Chemicals Co., Ltd.; and trade name “ESI40” and“ESI48” manufactured by Colcoat Co., Ltd.) and a partial hydrolyticcondensate between tetramethoxysilane and tetraethoxysilane (trade name“FR-3” manufactured by Tama Chemicals Co., Ltd.; and trade name “EMSi48”manufactured by Colcoat Co., Ltd.).

The mass ratio ((A1+A2)/B) of the total content of the component (A1)and the component (A2) to the content of the component (B) is notparticularly limited; however, in view of total light transmittance andinfrared absorption, the mass ratio is preferably 60/100 to 1000/100,more preferably 100/100 to 500/100 and further preferably 120/100 to300/100.

The mass ratio ((A2)/(B+A1)) of the content of the component (A2) to thetotal content of the component (B) and the component (A1) is, in view oftotal light transmittance of the coating film, preferably 0.05/100 to40/100, more preferably 0.1/100 to 20/100 and further preferably 0.1/100to 10/100.

The mass ratio ((b2)/(B)) of the content of the component (b2) to thecontent of the component (B) is, in view of polymerization stability,preferably 0.01/1 to 1/1, more preferably 0.1/1 to 0.8/1 and furtherpreferably 0.2/1 to 0.5/1.

The mass ratio ((b2)/(A)) of the content of the component (b2) to thecontent of the component (A) is, in view of improving hydrogen bondingability to a meal oxide, preferably 0.01/1 to 1/1, more preferably0.05/1 to 0.8/1 and further preferably 0.1/1 to 0.4/1.

Since the component (A2) relatively causes secondary coagulation moreeasily than the component (A1), if the mass ratio ((A2)/(A1+B)) of thecontent of the component (A2) to the total content of the component (B)and the component (A1) is set to be 40/100 or less, the transparency ofa coating film can be increased and a reduction of light transmittanceby scattering can be suppressed. If the ratio ((A2)/(A1+B)) of thecontent of the component (A2) to the total content of the component (B)and the component (A1) is set to be 0.05/100 or more, infraredabsorption by the coating-film surface can be increased and atemperature increase of silicon can be suppressed, thereby improvingpower generation efficiency.

The mass ratio ((A)/(B)) of the component (A) to the component (B) is,in view of hydrophilicity and film formation properties, preferably110/100 to 480/100, more preferably 110/100 to 300/100 and furtherpreferably 150/100 to 250/100. If the ratio is set to be the aboverange, antifouling properties, transparency and hydrophilicity can befurther improved and shock resistance/durability and the hydrophilicityof the coating-film surface at high temperature, high humidity orhigh-temperature/high-humidity can be rendered to be superior.

The mass ratio ((C)/(A)) of the component (C) to the component (A) ispreferably 1/100 to 150/100, more preferably 10/100 to 120/100 andfurther preferably 40/100 to 120/100. If the ratio of (C)/(A1) is 1/100or more, hydrophilicity tends to be maintained even under hightemperature conditions and high humidity conditions. If the ratio of(C)/(A) is 150/100 or less, the shock resistance of the resultantcoating film tends to be possibly more improved.

The component (A) preferably comprises silica having a number averageparticle size of 1 nm to 400 nm as the component (A1) and an infraredabsorbent having a number average particle size of 1 nm to 2000 nm asthe component (A2). The component (A1), while interacting with thecomponent (B), can be present between particles of the component (B) inthe form of a continuous phase. As a result, silica particles havinghigh hydrophilicity are present in the outermost surface of the coatingfilm. Therefore, high hydrophilicity can be obtained immediately afterformation of the coating film regardless of light irradiation, andsimultaneously, heat resistance, transparency and weather-resistance canbe more improved. In this case, it is preferable that the mass ratio((A1+A2)/(B)) of the total content of the component (A1) and thecomponent (A2) to the content of the component (B) is preferably 60/100to 1000/100 and that the mass ratio ((A2)/(A1+B)) of the content of thecomponent (A2) to the total content of the component (B) and thecomponent (A1) is preferably 0.05/100 to 40/100.

The component (A) preferably comprises component (A1): silica having anumber average particle size of 1 nm to 400 nm and component (A3): aphotocatalyst having a number average particle size of 1 nm to 2000 nm.The component (A1), while interacting with the component (B), can bepresent between particles of the component (B) in the form of acontinuous phase. As a result, silica particles having highhydrophilicity are present in the outermost surface of the coating film.Therefore, high hydrophilicity can be obtained immediately afterformation of the coating film regardless of light irradiation, andsimultaneously, transparency and weather-resistance can be moreimproved. In this case, the mass ratio ((A1+A3)/(B)) of the totalcontent of the component (A1) and the component (A3) to the component(B) is 60/100 to 480/100 and the mass ratio ((A1)/(A1+A3)) of thecontent of the component (A1) to the total content of the component (A1)and the component (A3) is more preferably 85/100 to 99/100.

(Application of Coating Composition)

The coating film resulting from the coating composition of theembodiment is excellent in antifouling properties, transparency,hydrophilicity and durability (shock resistance) and further canmaintain surface hydrophilicity even at high temperature, high humidityor high-temperature/high-humidity. Because of this, the coatingcomposition can be preferably used in various applications. In additionto these properties, other properties can be added if necessary asdescribed above, and thus, the coating composition can be preferablyused in various applications, for example, antireflection use, solventresistance use, antistatic use, heat resistance use and hard coatinguse.

(The Case of Antireflection Coating Composition)

In the coating composition of the embodiment, the curing time is notexcessively long and restriction on the types of substrates to be usedcan be eased. Furthermore, the resultant coating film is excellent inlight resistance, abrasion resistance and excellent durability. Sincethese advantages can be added, the coating composition of the embodimentcan be suitably used as an antireflection coating composition. Theantireflection coating composition can be preferably used in variousdisplay panels such as a liquid crystal display panel, a coldcathode-ray tube panel and a plasma display, displays used in the openair such as an advertising display and electrical scoreboards, as anantireflection film for preventing reflection of outer light andsimultaneously improving image quality.

A preferable aspect of an antireflection coating composition and membersusing the same will be described below. If the composition furthersatisfies the following conditions, not only properties such asantifouling properties, transparency and hydrophilicity but alsoantireflection performance can be added to the resultant coating film.

(1)

It is preferable that the antireflection coating composition comprises

as the component (A), a metal oxide having a number average particlesize of 1 nm to 400 nm, and

as the component (B), a polymer emulsion particle having a numberaverage particle size of 10 nm to 800 nm, in which

the component (B) is a polymer emulsion particle obtained bypolymerizing a polymerization material solution containing thecomponents (b1) to (b4); and

the mass ratio ((A)/(B)) of the component (A) to the component (B) is50/100 to 450/100.

Particularly, the component (A) that is used is preferably at least oneselected from the group consisting of silica (A1), a photocatalyst (A3)and a conductive metal oxide (A4) as mentioned above. Advantagesobtained by using these components are as mentioned above. In additionto this, in the case where the photocatalyst (A3) is used, photocatalystactivity and hydrophilicity can be exhibited by light irradiation. As aresult, an excellent activity to decompose organic staining substancesand fouling resistance of the coating surface can be furthersignificantly exhibited.

(2)

In the above item (1), it is preferable that the mass ratio ((b2)/(B))of the component (b2) to the component (B) is 0.1/1 to 0.5/1.

(3)

In the above item (1) or (2), it is preferable that the mass ratio((b2)/(A)) of the component (b2) to the component (A) is 0.1/1 to 1/1.

(4)

In any one of the above items (1) to (3), it is preferable that thecomponent (B) has a core/shell structure having a core layer and one ortwo or more shell layers covering the core layer.

(5)

In the core layer according to the above item (4), it is preferable thatthe mass ratio ((b2)/(b1)) of the component (b2) to the component (b1)is 0.01/1 to 1/1, and that the mass ratio ((b2)/(b1)) of the component(b2) to the component (b1) in the outermost shell layer is 0.1/1 to 5/1.

(6)

In the above item (4) or (5), it is preferable that the component (B)can be obtained by polymerizing a polymerization material solution inthe presence of a seed particle forming a core layer and that the seedparticle is obtained by polymerizing at least one selected from thegroup consisting of the component (b1), component (b2) and a vinylmonomer copolymerizable with the component (b2).

(7)

In any one of the above items (1) to (6), it is preferable that thecomponent (b2) is a vinyl monomer having a secondary amide group, atertiary amide group or both of them.

(8)

In any one of the above items (1) to (7), it is preferable that theparticle size of the component (B) is 120 to 450 nm.

(9)

In any one of the above items (1) to (8), it is preferable that theaforementioned component (C) is further contained.

(10)

An antireflection composite can be provided from the antireflectioncoating composition.

(11)

An antireflection composite containing the antireflection coatingcomposition can be provided.

(12)

A display containing the antireflection composite can be provided.

(13)

An exterior display member containing the antireflection composite canbe provided.

(The Case of Solvent Resistant Coating Composition)

In the coating composition of the embodiment, since the component (A)and the component (B) tend to interact with each other, the resultantcoating film is excellent in not only antifouling properties,transparency and hydrophilicity but also in weather resistance and thelike. Because of these advantages thus added, the coating compositioncan be preferably used also as a solvent resistant coating composition.An industrial product is generally washed with a solvent such as analcohol in a manufacturing step and product assembly and installationstep. Therefore, solvent resistance is required. In the case of, forexample, optical parts such as an optical lens, surface stain is wipedout with isopropyl alcohol and the like. At that time, if optical partsdo not have solvent resistance, the surface is dissolved and opticalcharacteristics such as transparency deteriorate. Therefore, the coatingcomposition of the embodiment can be preferably used as a coatingcomposition for adding solvent resistance to such a product.

A preferable aspect of the solvent resistant coating composition and amember using the same will be described below. If the compositionfurther satisfies the following conditions, not only transparency,hydrophilicity, antifouling properties and the like but also solventresistance can be added to the resultant coating film.

(1)

It is preferable that the solvent resistant coating compositioncomprises

as the component (A), a metal oxide having a number average particlesize of 1 nm to 400 nm, and

as the component (B), a polymer emulsion particle having a numberaverage particle size of 10 nm to 800 nm, in which the component (B) isa polymer emulsion particle obtained by polymerizing a polymerizationmaterial solution containing the components (b1) to (b4); and

the mass ratio ((A)/(B)) of the component (A) to the component (B)50/100 to 300/100.

(2)

In the above item (1), it is preferable that the mass ratio ((b2)/(B))of the component (b2) to the component (B) is 0.1/1 to 0.5/1.

(3)

In the above item (1) or (2), it is preferable that the mass ratio((b2)/(A)) of the component (b2) to the component (A) is 0.1/1 to 1/1.

(4)

In any one of the above items (1) to (3), it is preferable that thecomponent (B) has a core/shell structure having a core layer and one ortwo or more shell layers covering the core layer.

(5)

In the core layer according to the above item (4), it is preferable thatthe mass ratio ((b2)/(b1)) of the component (b2) to the component (b1)is 0.01/1 to 1/1, and that the mass ratio ((b2)/(b1)) of the component(b2) to the component (b1) in the outermost shell layer is 0.1/1 to 5/1.

(6)

In the core layer according to the above item (4) or (5), it ispreferable that the component (B) can be obtained by polymerizing apolymerization material solution in the presence of a seed particleforming a core layer and that the seed particle is obtained bypolymerizing at least one selected from the group consisting of thecomponent (b1), component (b2) and a vinyl monomer copolymerizable withthe component (b2).

(7)

In any one of items (1) to (6), it is preferable that the component (b2)is a vinyl monomer having a secondary amide group, a tertiary amidegroup or both of them.

(8)

In any one of items (1) to (7), it is preferable that the number averageparticle size of the component (B) is 20 to 250 nm.

(9)

In any one of items (1) to (8), it is preferable that the component (C)is further contained.

(10)

A solvent resistant composite can be provided from the solvent resistantcoating composition.

(11)

A solvent resistant composite containing the solvent resistant coatingcomposition can be provided.

(12)

A display containing the solvent resistant composite can be provided.

(13)

An exterior display member containing the solvent resistant compositecan be provided.

(14)

A transparent plastic for a window containing the solvent resistantcomposite can be provided.

(15)

A transparent protective material for photovoltaic power generationcontaining the solvent resistant composite can be provided.

(The Case of Antistatic Coating Composition)

In the coating composition of the embodiment, since a conductive metaloxide can be used as the component (A), antistatic properties can beadded to the resultant coating film. By virtue of this, the coatingcomposition of the embodiment can be used as an antistatic coatingcomposition. A preferable aspect of the antistatic coating compositionand a member using the same will be described below. Particularly, asthe component (A), at least one selected from the group consisting ofsilica (A1), photocatalyst (A3) and conductive metal oxide (A4) asmentioned above is more preferably used. Advantages of using thesecomponents are as mentioned above. If the following conditions aresatisfied, not only antifouling properties, transparency, hydrophilicityand the like but also antistatic performance can be added to theresultant coating film.

(1) It is preferable that the antistatic coating composition preferablycomprises

as the component (A), a metal oxide having a number average particlesize of 1 nm to 400 nm, and

as the component (B), a polymer emulsion particle having a numberaverage particle size of 10 nm to 800 nm, in which

the component (B) is a polymer emulsion particle obtained bypolymerizing a polymerization material solution containing thecomponents (b1) to (b4); and

the mass ratio ((A)/(B)) of the component (A) to the component (B) is150/100 to 450/100.

(2)

In the above item (1), it is preferable that the mass ratio ((b2)/(B))of the component (b2) to the component (B) is 0.1/1 to 0.5/1.

(3)

In the above item (1) or (2), it is preferable that the mass ratio((b2)/(A)) of the component (b2) to the component (A) is 0.1/1 to 1/1.

(4)

In any one of the above items (1) to (3), it is preferable that thecomponent (B) has a core/shell structure having a core layer and one ortwo or more shell layers covering the core layer.

(5)

In the core layer according to above item (4), it is preferable that themass ratio ((b2)/(b1)) of the component (b2) to the component (b1) is0.01/1 to 1/1, and that the mass ratio ((b2)/(b1)) of the component (b2)to the component (b1) in the outermost shell layer is 0.1/1 to 5/1.

(6)

In the core layer formed of the antistatic coating composition accordingto item (4) or (5), it is preferable that the component (B) can beobtained by polymerizing a polymerization material solution in thepresence of a seed particle forming a core layer, and that the seedparticle is obtained by polymerization of at least one selected from thegroup consisting of the component (b1), component (b2) and a vinylmonomer copolymerizable with the component (b2).

(7)

In any one of items (1) to (6), it is preferable that the component (b2)is a vinyl monomer having a secondary amide group, a tertiary amidegroup or both of them.

(8)

In any one of items (1) to (7), it is preferable that the number averageparticle size of the component (B) is 50 to 350 nm.

(9)

In any one of items (1) to (8), it is preferable that the component (C)mentioned above is further contained in the antistatic coatingcomposition, in which

the mass ratio ((A)/(B)) of the component (A) to the component (B) is150/100 to 350/100 and the mass ratio ((C)/(A)) of the component (A) tothe component (C) is preferable 0.5/100 to 110/100.

(10)

An antistatic composite can be provided from the antistatic coatingcomposition.

(11)

An antistatic composite containing the antistatic coating compositioncan be provided.

(12)

A display containing the antistatic composite can be provided.

(13)

An exterior display member containing the antistatic composite can beprovided.

(14)

A transparent plastic for a window containing the antistatic compositecan be provided.

(15)

A transparent protective material for photovoltaic power generationcontaining the antistatic composite can be formed.

(The Case of Heat Resistant Coating Composition)

In the coating composition of the embodiment, since an infraredabsorbent (A2) can be used as the component (A), heat resistanceperformance/thermal insulation performance can be also added to theresultant coating film. By virtue of this, the coating composition ofthe embodiment can be used also as a thermal insulation coatingcomposition. Particularly, as the component (A), it is more preferableto use at least one selected from the group consisting of silica (A1),the infrared absorbent (A2), the photocatalyst (A3) and the conductivemetal oxide (A4). Advantages of using these components are as mentionedabove. If the following conditions are satisfied, not only transparency,hydrophilicity, antifouling properties and the like but also heatresistance/thermal insulation performance can be added to the resultantcoating film.

(1)

A heat resistant coating composition comprises

as the component (A1), silica having a number average particle size of 1nm to 400 nm,

as the component (A2), an infrared absorbent having a number averageparticle size of 1 nm to 2000 nm, and

as the component (B), a polymer emulsion particle having a numberaverage particle size of 10 nm to 800 nm.

(2)

In the above item (1), it is preferable that the component (A2) is atleast one selected from the group consisting of indium oxide doped withtin, tin oxide doped with antimony, and cerium oxide or zinc oxideoptionally coated with silica.

(3)

In the above item (1) or (2), it is preferable that the component (B) isa polymer emulsion particle obtained by polymerizing, in apolymerization material solution containing the component (b1) tocomponent (b4), the component (b1) and the component (b2).

(4)

In any one of the above items (1) to (3), it is preferable that the massratio ((A1+A2)/(B)) of the total content of the component (A1) and thecomponent (A2) to the content of the component (B) is 60/100 to1000/100; and

the mass ratio ((A2)/(B+A1)) of the content of the component (A2) to thetotal content of the component (B) and the component (A1) is 0.05/100 to40/100.

(5)

In the above items (1) to (4), it is preferable that the mass ratio((b2)/(B)) of the content of the component (b2) to the content of thecomponent (B) is 0.1/1 to 0.5/1.

(6)

In the above items (1) to (5), it is preferable that the mass ratio((b2)/(A1)) of the content of the component (b2) to the content of thecomponent (A1) is 0.1/1 to 1/1.

(7)

In the above items (1) to (6), it is preferable that the component (B)has a core/shell structure having a core layer and one or two or moreshell layers covering the core layer.

(8)

In the core layer of the above item (7), it is preferable that the massratio ((b2)/(b1)) of the content of the component (b2) to the content ofthe component (b1) is 0.01/1 to 1/1; and

in the outermost shell layer, the mass ratio ((b2)/(b1)) of the contentof the component (b2) to the content of the component (b1) is 0.1/1 to5/1.

(9)

In the above item (7) or (8), it is preferable that the component (B) isa polymer emulsion particle obtained by polymerizing the component (b1)and the component (b2) in a polymerization material solution containinga seed particle forming the core layer; and

the seed particle is obtained by polymerizing at least one selected fromthe group consisting of the component (b1), component (b2), component(b5): a vinyl monomer copolymerizable with the component (b2).

(10)

In the above items (3) to (9), it is preferable that the component (b2)is a vinyl monomer having a secondary amide group, a tertiary amidegroup or both of them.

(11)

In the above items (1) to (10), it is preferable that a component (C) isfurther contained, and the mass ratio ((C)/(A1)) of the content of thecomponent (C) to the content of the component (A1) is preferably 1/100to 100/100.

(12)

In the above items (1) to (11), it is preferable that the component (B)has a number average particle size of 10 to 100 nm.

(13)

In the above items (1) to (12), it is preferable that the component (A1)is colloidal silica having a number average particle size of 1 nm to 400nm.

(14)

In the above items (1) to (13), it is preferable that the component (A2)has an absorbance of 0.1% or more within the wavelength region of 1000nm to 2500 nm.

(15)

A solar cell member having a substrate and a coating film formed byapplying the heat resistant coating composition onto the substrate,followed by drying can be provided. The solar cell member can be used asa solar cell protective member.

(The Case of Coating Composition for Hard Coating)

In the coating composition of the embodiment, curing time is notexcessively long and restriction on the types of substrates to be usedcan be eased. Furthermore, the resultant coating film is excellent inlight resistance, abrasion resistance and durability. Since theseadvantages can be added, the coating composition of the embodiment canbe preferably used also as a coating composition for hard coating. Apreferable aspect of the coating composition for hard coating andmembers using the same will be described below. If the followingconditions are satisfied, not only antifouling properties, transparency,hydrophilicity and the like but also hard coating performance can beadded to the resultant coating film.

(1)

It is preferable that the coating composition for hard coating comprises

as the component (A), a metal oxide having a number average particlesize of 1 nm to 400 nm, and

as the component (B), a polymer emulsion particle having a numberaverage particle size of 10 nm to 800 nm, in which

the component (B) is a polymer emulsion particle obtained bypolymerizing a polymerization material solution containing thecomponents (b1) to (b4); and

the mass ratio ((A)/(B)) of the component (A) to the component (B) is50/100 to 350/100.

(2)

In the above item (1), it is preferable that the mass ratio ((b2)/(B))of the component (b2) to the component (B) is 0.1/1 to 0.5/1.

(3)

In the above item (1) or (2), it is preferable that the mass ratio((b2)/(A)) of the component (b2) to the component (A) is 0.1/1 to 1/1.

(4)

In any one of the above items (1) to (3), it is preferable that thecomponent (B) has a core/shell structure having a core layer and one ortwo or more shell layers covering the core layer.

(5)

In the core layer according to the above item (4), it is preferable thatthe mass ratio ((b2)/(b1)) of the component (b2) to the component (b1)is 0.01/1 to 1/1, and that the mass ratio ((b2)/(b1)) of the component(b2) to the component (b1) in the outermost shell layer is 0.1/1 to 5/1.

(6)

In the above item (4) or (5), it is preferable that the component (B)can be obtained by polymerizing a polymerization material solution inthe presence of a seed particle forming a core layer, and that the seedparticle is obtained by polymerizing at least one selected from thegroup consisting of the component (b1), component (b2) and a vinylmonomer copolymerizable with the component (b2).

(7)

In any one of the above items (1) to (6), it is preferable that thecomponent (b2) is a vinyl monomer having a secondary amide group, atertiary amide group or both of them.

(8)

In any one of items (1) to (7), it is preferable that the number averageparticle size of the component (B) is 50 to 250 nm.

(9)

In any one of the above items (1) to (8), it is preferable that thecomponent (C) mentioned above is further contained and the mass ratio((A)/(B)) of the component (A) to the component (B) is 50/100 to350/100, and the mass ratio ((C)/(A)) of the component (A) to thecomponent (C) is 5/100 to 90/100.

(10)

A hard coating composite can be provided from the coating compositionfor hard coating.

(11)

A hard coating composite containing the coating composition for hardcoating can be provided.

(12)

A display containing the hard coating composite can be provided.

(13)

An exterior display member containing the hard coating composite can beprovided.

(14)

A traffic window containing the hard coating composite can be provided.

(15)

A transparent protective material for use in photovoltaic powergeneration containing the hard coating composite can be provided.

A coating film can be obtained from the coating composition of theembodiment. A method for forming the coating film of the embodiment isnot limited and a known method for forming a coating film from a coatingsolution can also be employed. For example, a coating film can be formedby applying a coating composition dispersed in water, an organic solventand the like onto an object on which the film is to be formed (forexample, a substrate) followed by drying. More specifically, a coatingfilm having a plurality of layers can be also formed by repeating aprocess of applying the coating composition followed by drying. In thiscase, a coating composition is first applied onto e.g., a substrate anddried to obtain a single layer. Thereafter, the coating composition isfurther applied onto the layer (i.e., recoating) and dried to formanother layer, and if necessary, this operation is repeated. Byemploying such a method, the coating film having a plurality of layersstacked can be obtained.

Another aspect of the coating film of the embodiment, there is provideda coating film having a metal oxide particle (A) and a polymer particle(B) surrounded by the component (A), in which the surface of a filmformed of component (B2) extracted from the component (B) byultrafiltration and having a molecular cutoff of 50,000 or less has awater contact angle of 30° or less.

It is satisfactory if the surface of a dry film formed of component (B2)extracted from the component (B) and having a molecular cutoff of 50,000or less has a surface contact angle with water of larger than 30° at 20°C., and the compositions and the like of component (A), component (B)and component (B2) are not particularly limited. For example, theaforementioned component (A) and component (B) may be employed. Thesurface contact angle used herein refers to an angle between the dryfilm and a tangent line of a water drop present on the surface and canbe measured by a drop method.

In the coating film, it is preferable that the content of the component(B2) is 5 mass % or less. If the content of the aforementionedaqueous-phase component is controlled to be 5 mass % or less, thedistribution coefficient to a water medium falls within a predeterminedrange. As a result, high surface hydrophilicity can be maintained evenat high temperature, high humidity and further at high temperature/highhumidity.

In the coating film of the embodiment, a polymer particle (B) may besurrounded by a metal oxide particle (A). As a dispersion structure, asea-island structure is preferred. To describe more specifically thecomponent (A) may present like a sea phase, whereas the component (B)may present like an island phase. It is preferable that the component(A) is present between the particles of the component (B) in the form ofa continuous phase, while mutually interacting with the component (B).In this case, the reflectivity, weather resistance and antifoulingproperties of the resultant coating composition can be improved.

Furthermore, the component (B) is preferably the aforementioned emulsionparticle. The emulsion particle is preferably the aforementioned polymeremulsion particle (B1). As the emulsion particle or polymer emulsionparticle, the aforementioned ones can be used.

A preferable aspect of the embodiment is a coating film having a watercontact angle with a surface of 20° at 20° C.

Furthermore, after a high-temperature/high-humidity test in which a filmis allowed to stand still at 90° C. under the conditions of a humidity90% for 24 hours, the water contact angle of the coating-film surface ispreferably 20° or less. After the high-temperature/high-humidity test,the water contact angle of the coating-film surface is measured by themethod described in Examples described later. The temperature andhumidity to be used in the test, can be controlled by a method using aknown high-temperature/high-humidity tester, for example, SH-661manufactured by ESPEC Corp. Alternatively, a sealed container chargedwith distilled water, heated at a predetermined temperature to producesaturated vapor, which is used for evaluation.

<Laminate>

A laminate can be obtained from the coating film and coating compositionof the embodiment. FIG. 1 is a schematic sectional view of a laminateaccording to the embodiment. A laminate 1 of the embodiment has asubstrate 10 and a coating film 12, which is formed by applying theaforementioned coating composition onto at least one of the surfaces ofthe substrate 10.

Examples of a method for forming a coating film using the coatingcomposition of the embodiment include, but not particularly limited to,a method for forming a coating film by applying a coating compositiononto a substrate followed by drying. In this case, the solid contentconcentration of the coating composition is preferably 0.01 to 60 mass %and more preferably 1 to 40 mass %. The viscosity (20° C.) of thecoating composition is preferably 0.1 to 100000 mPa·s and morepreferably 1 to 10000 mPa·s.

Examples of a coating method of applying a coating composition to asubstrate include, but not particularly limited to, a spray method, aflow coating method, a roll coating method, a bar coating method, abrush coating method, a dip coating method, a spin coating method, ascreen coating method, a casting method, a gravure printing method, anda flexo printing method. Regarding the laminate of the embodiment, aftera coating film is formed on a substrate, if desired, a heat treatmentand UV rays may be applied. The temperature of the heat treatment is notparticularly limited; however, the temperature is preferably 20° C. to500° C. and more preferably 40° C. to 250° C.

In the embodiment, the coating film may have a single layer or two ormore layers. A plurality of layers are preferable since a plurality offunctions can be added to a laminate. A laminate having a plurality ofcoating films is formed, for example, by a recoating method for acoating composition as mentioned above.

The substrate is not particularly limited; however, it preferablycontains at least one selected from the group consisting of glass, anacrylic resin, a polycarbonate resin, a cyclic polyolefin resin, apolyethylene terephthalate resin and an ethylene-fluoroethylenecopolymer. From these resins, a preferable material can be appropriatelyselected depending upon desired properties. More specifically, in viewof transparency, weather resistance and reduction in weight, it ispreferable to use at least one selected from the group consisting ofglass, an acrylic resin, a polycarbonate resin, a cyclic olefin resin, apolyethylene terephthalate resin and an ethylene-fluoroethylenecopolymer or a composite material of these. Furthermore, in view ofadding weather-resistance, a weather resistant agent and the like may befurther kneaded in an acrylic resin, a polycarbonate resin, a cyclicpolyolefin resin, a polyethylene terephthalate resin and anethylene-fluoroethylene copolymer. The substrate may be formed of asingle layer and a plurality of layers.

The thickness of the coating film is preferably 0.05 μm to 100 μm andmore preferably 0.1 μm to 10 μm. In view of transparency, the thicknessis preferably 100 μm or less. To exert a function such asweather-resistance and antifouling properties, the thickness ispreferably 0.05 μm or more.

In the case where a coating film is formed of two or more layers, thethickness (dn) of each layer is preferably 10 nm to 800 nm, and thetotal thickness (Σdn) of the coating film is more preferably 100 nm to4000 nm. If the thickness ratio falls within the above range, higherlight transmittance than that of a substrate and a singly-layer coatingfilm can be obtained. If any one of the multiple layers has a thickness(dn) of 10 nm or more, the film thickness can be easily controlled. Evenif a coating film is formed on an uneven substrate surface, theunevenness of the coating film can be effectively suppressed.Furthermore, if any one of the layers has a thickness (dn) of 800 nm orless, high light transmittance can be maintained. The total thickness(Σdn) of multiple layers varies depending upon the thickness of each ofthe layers constituting the coating film. If the total thickness (Σdn)is 100 nm or more, the thickness of a single layer can be ensured andthus, the film thickness can be easily controlled. Furthermore, if thetotal thickness (Σdn) of the multiple layers is 4000 nm or less, highlevel light transmittance can be exhibited compared to a coating filmformed of a single layer having the same film thickness.

In the case where a coating film (laminate) formed of two or morelayers, a laminate having the total thickness (Σdn) of the coating filmin the range of 100 nm to 4000 nm and the thickness (dn) of each layerin the range of 10 nm to 800 nm layer is obtained by, for example, amethod of suppressing a solid content concentration in a coatingcomposition of the embodiment and serving as a raw material, forexample, within 1 to 10 mass %. If the solid content concentration issuppressed within the above range, the total thickness of the coatingfilm can be controlled within the above range.

The present inventors have intensively studies about the thickness of alayer of a coating-film laminate formed of a plurality of layers and thelike. As a result, they found that if the thickness (dn and Σdn) of thecoating film layer is set to fall within in the range, lighttransmittance higher than that of the substrate and a single-layercoating film can be obtained. Furthermore, they found that the coatingcomposition serving as a raw material for a coating film is diluted withwater so as to obtain a solid content concentration of, preferably, 1 to10 mass %, the light transmittance can be effectively improved. Thereasons of these are not yet elucidated in detail; however, one of thereasons is conceivably as follows.

More specifically, to obtain a coating film having the aforementionedlayer thickness, it is desirable that the solid content concentration ofa coating composition as raw material is reduced up to, for example, 1to 10 mass %. This is because if the solid content concentration is setto fall within the aforementioned range, the total thickness of alaminate consisting of a plurality of layers can fall within the range.In contrast, the component (A), the component (B) and the likeconceivably have a concentration and pH at which a solid particle ispresent in a stably dispersed state; however, if the coating compositionis diluted preferably rapidly with water or a dilution solvent such asan alcohol, it is presumable that the dispersion state is no longerstable and a certain type of association and soft aggregate are formed.Then, if a coating film consisting of a plurality of layers is formed byusing a coating composition having an association and a soft aggregationstably formed therein, e.g., the porosity of the coating film increases.Hence, light transmittance conceivably increases.

In the embodiment, it is preferable that the light transmittance of alaminate is higher than light transmittance of the substrate. By virtueof this, if such a laminate is used as a member of an energy conversionapparatus such as a solar cell, energy output of the energy conversionapparatus such as a solar cell can be improved. Note that lighttransmittance in the embodiment is measured in accordance with themethod described in Examples described later. The light transmittance ofa substrate is preferably 30% to 99%, more preferably, 70% to 99% andfurther preferably 80% to 99%. If the light transmittance of a substratefalls within the range, a solar cell having a practically high outputcan be obtained. The light transmittance can be measured in accordancewith JIS K7105.

In the embodiment, it is preferable that the refractive index of thecoating film is 0.1 or more lower than the refractive index of thesubstrate. By virtue of this, the light transmittance can be improved.In the case where the coating film has two or more layers, it ispreferable that the refractive index of the outermost surface layer uponwhich sunlight is incident is 0.1 or more lower than the refractiveindex of the layer adjacent to the outermost surface layer. By virtue ofthis, refractive index decreases stepwise from a sunlight incident sidetoward a substrate. As a result, reflection upon the coating-filmsurface is suppressed and the light transmittance can be improved.Reflectivity is measured in accordance with the method described inExamples described later.

In the embodiment, it is preferable that difference in refractive indexbetween the coating film and the substrate is 0.2 or less. If thedifference in refractive index falls within the range or less, the samerefractive properties as that of the substrate can be obtained. As aresult, reflectivity can be increased to efficiently collect solar heat.The refractive index is measured in accordance with the method describedin Examples described later.

In the embodiment, the refractive index of the coating film ispreferably 1.30 to 1.48 and more preferably 1.34 to 1.43. Furthermore,it is preferable that both the refractive index of the coating film andthe refractive index of the outermost surface layer fall within therange mentioned above. The refractive indexes of the coating film andthe outermost surface layer can be selected depending upon the type ofsubstrate, thickness and shape. If the refractive index of the coatingfilm is 1.30 or more, the strength of the coating film tends toincrease. If the refractive index of the coating film is 1.48 or less,light scattering can be suppressed and in particular, a haze value tendsto be possibly reduced.

The ratio (Rb/Rc) of reflectivity (Rc) of the surface (S1) of a coatingfilm opposite to a substrate to reflectivity (Rb) of the surface (S2) ofthe substrate on the coating film side is preferably 98% or more, morepreferably 99.5% or more and further preferably, 99.7% or more (see FIG.1). Furthermore, a reduction rate ((Rb−Rc)/Rb) of reflectivity (Rc) toreflectivity (Rb) is preferably 2% or less, preferably 0.5% or less, andmore preferably 0.3% or less.

In the case where a laminate is obtained by recoating to have a filmwith a predetermined thickness obtained by coating, the reflectivity(Rc) of the coating film tends to be lower than the reflectivity (Rb) ofthe substrate by light absorption by the coating film itself, lightscattering in the interface between the substrate and the coating filmand between mutual coating films and the like. In particular, if asubstrate having a high reflectivity (Rb) is used, the tendency issignificant. The laminate of the embodiment using an organic/inorganiccomposite coating film, even if coating films are stacked repeatedly byrecoating, a reduction rate of reflectivity (Rc) to reflectivity (Rb)can be suppressed within 2% or less. The reflectivity may furtherreduce; however it is preferably 2% or less in view of energyefficiency.

Furthermore, it is preferable that the reflectivity (Rb) is 80% or more.By virtue of this, sunlight can be efficiently collected and powergeneration cost of an apparatus can be reduced.

As the method for manufacturing a laminate according to the embodiment,any method may be used as long as a coating film is formed on asubstrate, and a known method can be also employed. Preferably, it ispossible to employ a manufacturing method having the steps of forming acoating film on at least one of the surfaces of a substrate by applyingthe coating composition of the embodiment and applying a heat treatmentof 70° C. or more, a pressurization treatment at 0.1 kPa or more or bothof them to the coating film. In the step of forming a coating film usingthe coating composition of the embodiment, as a method for obtaining thecoating film of the embodiment, the aforementioned method can beemployed. Then, if the resultant coating film is subjected to a step ofapplying a heat treatment of 70° C. or more, a pressurization treatmentat 0.1 kPa or more or both of them, the coating film can be formed moredensely. A method for the heat treatment is not particularly limited andcan be performed by use of e.g., a known apparatus. A method forpressurization treatment is not particularly limited and can beperformed by use of e.g., a known apparatus.

<Member of Energy Conversion Apparatus>

The laminate of the embodiment can be preferably used as a member of anenergy conversion apparatus. Examples of the energy conversion apparatusinclude a power generation apparatus using sunlight. The member for anenergy refers to a member that can be used, for example, in powergeneration using sunlight. More specific examples thereof include amember for use in a solar cell module and a member for use in a solarthermal power generation system. More specifically, the laminate can beused in cover glass, which is a protective member for the surface of asolar cell module, a backsheet, which is a protective member for a rearsurface, a sealant, a mold frame such as an aluminum frame, Fresnel lensof a concentrator solar cell and a light reflecting mirror for use insolar thermal power generation.

Particularly, the laminate of the embodiment is preferably used as aprotective member for a solar cell module. For example, if a large scalesolar cell module is set up in desert and the like and used sandparticles and the like blown up by wind attach to the protective memberof the solar cell module, producing problems: the surface of the memberis scratched, transparency and the effect of antifouling propertiesdecrease. However, in the embodiment, the coating film of the laminateis excellent in antifouling properties, transparency, hydrophilicity anddurability (shock resistance) and surface hydrophilicity can bemaintained even at high temperature/high humidity, attached sandparticles, dust and the like can be easily washed out with e.g., rainwater.

<Solar Cell Module>

The laminate of the embodiment is used in a solar cell module as aprotective member (hereinafter, sometimes simply referred to as theprotective member) of solar cell module. FIG. 2 is a schematic sectionalview showing an aspect of a solar cell of the embodiment. In theembodiment, a solar cell module 2 has a protective member 20, abacksheet 22, which is arranged so as to face the protective member 20and a power generating element 24 arranged between the protective member20 and the backsheet 22. Furthermore, the power generating element 24 issealed by a sealant 26. In the solar cell module 2, sunlight L isincident on the protective member 20 and reaches the power generatingelement 24.

The protective member 20 is used for protecting the power generatingelement 24 and the like. The protective member 20 has a coating film 204formed on the surface of the substrate. In this case, the protectivemember 20 serves as light transmissible substrate through which sunlighttransmits and simultaneously can prevent a temperature increase of asolar cell module because the member is excellent in the aforementionedantifouling properties and infrared ray blocking properties. It is thuspreferable that the protective member 20 is used such that the surfaceon which the coating film 204 is formed corresponds to the surface sideof the solar cell module 2.

The protective member 20 preferably has performance ensuring long-termreliability of the solar cell module 2, such as weather resistance,water repellency, antifouling properties and mechanical strength eventhough it is exposed to outdoor air. Furthermore, the member ispreferably a highly transparent member while minimizing optical loss inorder to efficiently use sunlight. Examples of a substrate 202 are notparticularly limited and the aforementioned ones can be used. Specificexamples thereof include, a glass substrate; a resin film formed of apoly ester resin, a fluorine resin, an acrylic resin, a cyclic olefin(co) polymer, an ethylene-vinyl acetate copolymer and the like. Ofthese, in view of weather resistance, shock resistance and cost balance,a glass substrate is more preferable.

In the case where a glass substrate is used, it is preferable that thetotal light transmittance of light having a wavelength 350 to 1400 nm is80% or more and more preferably 90% or more. As such glass substrate, awhite crown glass plate having a low absorption of an infrared region isgenerally used. Even in the case of a soda lime glass plate, as long asit has a thickness of 3 mm or less, output characteristic of the solarcell module is usually less affected. Furthermore, if a heat treatmentis applied to enhance the mechanical strength of a glass substrate,strengthened glass can be obtained; however, float-plate glass to whichno heat treatment is applied may be used.

As the resin film, in view of transparency, strength, cost and the like,a polyester resin is preferable and particularly, a polyethyleneterephthalate resin is more preferable. Furthermore, a fluorine resinextremely excellent in weather resistance is preferably used. Specificexamples thereof include an ethylene tetrafluoride-ethylene copolymer(ETFE), a polyvinyl fluoride resin (PVF), polyvinylidene fluoride resin(PVDF), a polytetrafluoride ethylene resin (TFE), a tetrafluorideethylene-hexafluoride propylene copolymer (FEP) and a chlorotrifluoroethylene resin (CTFE). In view of weather resistance, a polyvinylidenefluoride resin is preferable. In view of maintaining both weatherresistance and mechanical strength, an ethylene tetrafluoride-ethylenecopolymer is preferable.

As the coating film 204, the aforementioned coating film can be used. Asa method for forming the coating film 204 on the substrate 202, theaforementioned method can be used.

The backsheet 22 is not particularly limited; however since it isarranged in the outermost surface layer of a solar cell module, thebacksheet preferably has various properties such as weather resistanceand mechanical strength similarly to the aforementioned protectivemember 20. Therefore, the backsheet may be formed of the same materialas used in the protective member 20. More specifically, theaforementioned various material that can be used for the protectivemember 20 (particularly, substrate 202) can be used for the backsheet.Particularly, a polyester resin and a glass substrate can be preferablyused. Of them, in view of weather-resistance and cost, a polyethyleneterephthalate resin (PET) is more preferable.

The backsheet 22 is designed on the assumption that no sunlight passestherethrough, transparency (light-transmitting properties) is notrequired although it is required for the protective member 20. Then, areinforcing sheet (not shown) may be attached in order to increasemechanical strength of the solar cell module 2 and prevent distortionand warpage caused by temperature change. For example, a steel board, aplastic board and an FRP (fiberglass reinforced with plastic) board canbe preferably used.

The backsheet 22 may have a multi-layer structure consisting of two ormore layers. As an example of the multi-layer structure, a structure inwhich one or two or more layers consisting of the same components aresymmetrically stacked on both sides of a central layer may be mentioned.Examples of such a structure include PET/alumina deposited PET/PET, PVF(trade name: Tedlar)/PET/PVF, and PET/AL foil/PET.

The power generating element 24 is not particularly limited as long asit generates power by use of photovoltaic effect of a semiconductor.Examples thereof that can be used include silicon (single crystalline,polycrystalline, amorphous silicon) and a compound semiconductor (3-5family, 2-6 family, and so forth). Of these, polycrystalline silicon ispreferable in view of balance between power generation performance andcost.

As the sealant 26, any member can be used as long as it can seal thepower generating element 24 and the type of sealant is not particularlylimited. Examples thereof include a resin sealant sheet containing aresin such as an ethylene-vinyl acetate copolymer (EVA). Such a resinsealant sheet, if it is melted by application of heat, tightly adheresto the power generating element 24 (object to be sealed) andsuccessfully seals it. If such a sealant is used, excellent adhesivenessto the protective member 20 and the backsheet 22 can be exerted whilepreventing creep of the power generating element.

A method for manufacturing the solar cell of the embodiment is notparticularly limited and a known method can be employed. For example,the solar cell can be manufactured by sequentially stacking theprotective member 20/sealant 26/power generating element 24/sealant26/backsheet 22 in this order, and subjecting the stacked layers to avacuum laminate process performed by a vacuum laminate apparatus underthe conditions of 150° C. for 15 minutes.

In the solar cell module 2, the thickness of each member is notparticularly limited; however, the thickness of the protective member 20is preferably 3 mm or more in view of weather-resistance and shockresistance; the thickness of the backsheet 22 is preferably 75 μm ormore in view of insulation; the thickness of the power generatingelement 24 is preferably 140 μm to 250 μm in view of balance betweenpower generation performance and cost; and the thickness of the sealant26 preferably 250 μm or more in view of cushioning properties andsealing properties.

<Reflector Device>

FIG. 3 is a schematic perspective view of a reflector device of theembodiment. A reflector device 3 has a light reflecting mirror 32, alaminate 30 of the embodiment formed on the reflecting surface side ofthe light reflecting mirror, a support 34 for supporting the reflectingmirror 32. The reflector device employs the laminate 30 of theembodiment as a protective member for the light reflecting mirror 32(hereinafter, sometimes simply referred to as the “protective member”).The structure of the reflector device 3 is not particularly limited andappropriately modified into a preferable structure.

<Solar Thermal Power Generation System>

In the embodiment, a solar thermal power generation system can beprovided, which has the reflector device and a conversion apparatus forconverting sunlight collected by the reflector device into electricalenergy. The structure of the solar thermal power generation system isnot particularly limited and appropriately modified into a preferablestructure.

EXAMPLES

The present invention will be more specifically described by way ofExamples and Comparative Examples, below. However, the present inventionis not limited to the examples below. Note that physical properties wereevaluated by the following methods. Note that in the examples, unlessotherwise specified, “%” and “parts” are based on mass.

Number average particle size

A number average particle size was measured by diluting a sample byadding a solvent such that the solid content in the sample was 0.1 to 20mass % and using a wet-process particle-size analyzer (MicrotrackUPA-9230 manufactured by Nikkiso Co., Ltd.).

Initial contact angle

A deionized water drop was placed on the surface (thecoating-composition applied surface) of a sample and allowed to standstill at 23° C. for one minute, and thereafter, an initial contact anglewas measured by a contact-angle measuring device (CA-X150 contact anglemeter manufactured by Kyowa Interface Science Co., Ltd.).

Initial haze/light transmittance

The haze value (initial haze value) of a sample was measured by use of aturbidimeter (NDH2000 manufactured by Nippon Denshoku Industries Co.,Ltd.) in accordance with JIS K7105. Note that light transmittance wasmeasured in accordance with JIS K7105.

Appearance of coating film

Appearance of a sample (coating-composition applied surface) wasobserved by a microscope (manufactured by Keyence Corporation;magnification: 100×). The results were evaluated as follows:

◯: Microcracks are rarely observed,Δ: Many microcracks are observed,×: Film cannot be formed.

Contact angle after heat resistance test After a sample was stored at70° C. for 10 days, a deionized water drop was placed on the coatingsurface and allowed to stand still at 23° C. for one minute, a contactangle was measured by a contact-angle measuring device (CA-X150 contactangle meter manufactured by Kyowa Interface Science Co., Ltd.).

Contact angle after high humidity test

After a sample was stored for 16 hours in SH-661 (manufactured by ESPECCorp.) set to 40° C. and 90% RH, a deionized water drop was placed onthe coating surface and allowed to stand still at 23° C. for one minute,and then a contact angle was measured by a contact-angle measuringdevice (CA-X150 contact angle meter manufactured by Kyowa InterfaceScience Co., Ltd.).

Contact angle after high-temperature/high-humidity storage

After a sample was allowed to stand still for 24 hours in SH-661(manufactured by ESPEC Corp.) set to 90° C. and 90% RH, a deionizedwater drop was placed on the coating surface and allowed to stand stillat 23° C. for one minute, and then a contact angle was measured by acontact-angle measuring device (CA-X150 contact angle meter manufacturedby Kyowa Interface Science Co., Ltd.).

Pencil hardness

The pencil hardness of a sample was measured by a pencil hardness meter(manufactured by Tester Sangyo Co., Ltd.).

Abrasion resistance test

The surface of a sample was rubbed reciprocally 10 times by a cottonswab with an application of a load of 500 g, and then a change wasvisually observed.

◯: Substantially no changeΔ: Slightly scratched×: Many scratches

Coating film reflectivity

The absolute reflectivity of a sample was measured by a reflectionspectroscopy film-thickness meter (FE3000 manufactured by OtsukaElectronics Co., Ltd.).

Antistatic properties

The surface resistance value of a surface was measured by a turbidimeter(NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).

Appearance after solvent resistance test

After a solvent-resistant composite was prepared, the coatingcomposition-applied surface of the solvent-resistant composite wasrubbed reciprocally 10 times by a cotton swab previously soaked inisopropyl alcohol with an application of a load of 500 g. The state of acoating film was observed by a microscope (manufactured by KeyenceCorporation; magnification: 100×). The results were evaluated asfollows:

◯: Microcracks are rarely observed,Δ: Microcracks are observed,×: Many cracks appear.

Heat resistance

A heat-resistant composite was formed and thereafter pressed against ahot plate of 150° C. for 10 minutes. Then, a haze value was measured bya turbidimeter (NDH2000 manufactured by Nippon Denshoku Industries Co.,Ltd.). The results were evaluated as follows:

◯: Haze 2,

Δ: 2<haze≦10,×: 10<haze.

Solvent resistance

A functional composite (coating film used in a Comparative Example) wasprepared. The surface thereof was rubbed reciprocally 10 times by acotton swab impregnated with acetone and then appearance of the surfacewas visually observed.

⊚: Rarely changed,◯: Slightly changed,Δ: Somewhat bleached,×: Significantly bleached.

Surface hardness

The pencil hardness of a sample (coating film used in a ComparativeExample) was measured by a pencil hardness meter (manufactured by TesterSangyo Co., Ltd.).

Laminate reflectivity

Using an UV-Vis/NIR Spectrophotometer (trade name “V-670” manufacturedby JASCO Corporation) and a large-scale integrating sphere meter, thereflectivity values of a substrate and a laminate were measured. Themeasurement was performed within the range of a wavelength of 350 nm to500 nm and the highest reflectivity value was employed as an evaluationvalue. In measuring the reflectivity of the laminate, as a substrate, amirror formed by depositing Al onto a 3 mm-thick soda lime glass wasused. The soda lime glass plate surface is coated with a coatingcomposition and reflectivity of light incident upon the coating-filmsurface was used as a measurement value.

Film thickness and refractive index

Using a film-thickness meter (trade name “FE-3000” manufactured byOtsuka Electronics Co., Ltd.), the film thickness of a coating-filmlaminate and the refractive indexes (wavelength: 633 nm) of the coatingfilm and the substrate were measured.

Contact angle after weather-resistance test

The coating films stacked on a substrate was subjected to aweather-resistance test by a xenon weather meter (manufactured by SugaTest Instruments Co., Ltd., cycle conditions: xenon lamp luminousintensity: 60 W/m², BPT 63° C., 50% RH, 102 minutes, rainfall, 30° C.,95% RH, 18 minutes) for 2500 hours. Subsequently, a deionized water dropwas placed on the coating-film surface, and allowed to stand still at23° C. for one minute, and then the contact angle of the water drop wasmeasured by a contact-angle measuring device (CA-X150 contact-anglemeter manufactured by Kyowa Interface Science Co., Ltd.).

Pore size, porosity

The coating-film surface was observed by use of an electron microscopeat a magnification of 250,000× to obtain the maximum diameter and widthof pores in the surface. Furthermore, a circumscribed circle equivalentdiameter was obtained. The volume of a coating film was obtained basedon the area of a 1000 nm-squares and a film thickness. Based on theresults, porosity was calculated.

Analysis of carbon amount (C/Si) of coating-film surface

The coating film formed on a substrate was made into pieces of about 3mm-squares, which were used as measurement samples. Measurement wasperformed by use of XPS (PHI Quantera SXM) in the conditions: anexcitation source: monoAlka, 15 kV x 6.7 mA, analysis size: 1.5 mm×100μm, intake region (survey scan; 0 to 1, 100 eV, Narrow scan; Si, 2p, C1s(K, 2p), 01s, Na1s, Ca2p, PassEnergy (survey scan; 200 eV, Narrow scan;112 eV). The results were obtained by normalizing the relativeconcentrations (atomic %) of individual elements based on Si element as1 to computationally obtain a C/Si ratio.

Production Example 1 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-1)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (150 g),tetraethoxysilane (30 g), phenyltrimethoxysilane (145 g) and3-methacryloxypropyltrimethoxysilane (1.3 g) and a solution mixture ofdiethylacrylamide (165 g), acrylic acid (3 g), a reactive emulsifier(trade name “ADEKA REASOAP SR-1025”, manufactured by ADEKA Corporation,an aqueous solution containing 25 mass % solid content) (13 g), a 2 mass% aqueous ammonium persulfate solution (40 g) and ion-exchanged water(1900 g) were simultaneously added dropwise over about two hours whilekeeping the temperature of the reaction vessel at 80° C. Furthermore,stirring was continued for about two hours while keeping the temperatureof the reaction vessel at 80° C. Thereafter, the temperature of thereaction vessel was cooled to room temperature and filtration wasperformed by a 100 mesh wire netting. The solid content concentrationwas controlled to be 10.0 mass % with ion-exchanged water to obtain awater dispersion of the polymer emulsion particle (HB-1) having a numberaverage particle size of 70 nm. The content of an aqueous-phasecomponent was 18 mass %.

Production Example 2 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-2)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (4.6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (86 g),phenyltrimethoxysilane (133 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (137 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, stirring was continued for abouttwo hours while keeping the temperature of the reaction vessel at 80° C.Thereafter, the temperature of the reaction vessel was cooled to roomtemperature and filtration was performed by a 100 mesh wire netting. Thesolid content concentration was controlled to be 10.0 mass % withion-exchanged water to obtain a water dispersion of the polymer emulsionparticle (HB-2) having a number average particle size of 100 nm. Thecontent of an aqueous-phase component was 18 mass %.

Production Example 3 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-3)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (2.6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (86 g),phenyltrimethoxysilane (133 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (137 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, stirring was continued for abouttwo hours while keeping the temperature of the reaction vessel at 80° C.Thereafter, the temperature of the reaction vessel was cooled to roomtemperature and filtration was performed by a 100 mesh wire netting. Thesolid content concentration was controlled to be 10.0 mass % withion-exchanged water to obtain a water dispersion of the polymer emulsionparticle (HB-3) having a number average particle size of 180 nm. Thecontent of an aqueous-phase component was 18 mass %.

Production Example 4 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-4)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (4 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (86 g),phenyltrimethoxysilane (133 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (137 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, stirring was continued for abouttwo hours while keeping the temperature of the reaction vessel at 80° C.Thereafter, the temperature of the reaction vessel was cooled to roomtemperature and filtration was performed by a 100 mesh wire netting. Thesolid content concentration was controlled to be 10.0 mass % withion-exchanged water to obtain a water dispersion of the polymer emulsionparticle (HB-4) having a number average particle size of 130 nm. Thecontent of an aqueous-phase component was 18 mass %.

Production Example 5 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-5)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (10 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (86 g),phenyltrimethoxysilane (133 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (137 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, stirring was continued for abouttwo hours while keeping the temperature of the reaction vessel at 80° C.Thereafter, the temperature of the reaction vessel was cooled to roomtemperature and filtration was performed by a 100 mesh wire netting. Thesolid content concentration was controlled to be 10.0 mass % withion-exchanged water to obtain a water dispersion of the polymer emulsionparticle (HB-5) having a number average particle size of 40 nm. Thecontent of an aqueous-phase component was 18 mass %.

Production Example 6 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-6)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (20 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (86 g),phenyltrimethoxysilane (133 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (137 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, stirring was continued for abouttwo hours while keeping the temperature of the reaction vessel at 80° C.Thereafter, the temperature of the reaction vessel was cooled to roomtemperature and filtration was performed by a 100 mesh wire netting. Thesolid content concentration was controlled to be 10.0 mass % withion-exchanged water to obtain a water dispersion of the polymer emulsionparticle (HB-6) having a number average particle size of 20 nm. Thecontent of an aqueous-phase component was 18 mass %.

Production Example 7 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-7)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C.

Subsequently, a solution mixture of butyl acrylate (150 g),tetraethoxysilane (30 g), phenyltrimethoxysilane (145 g) and3-methacryloxypropyltrimethoxysilane (1.3 g) and a solution mixture ofN-isopropylacrylamide (165 g), acrylic acid (3 g), a reactive emulsifier(trade name “ADEKA REASOAP SR-1025”, manufactured by ADEKA Corporation,an aqueous solution containing 25 mass % solid content) (13 g), a 2 mass% aqueous ammonium persulfate solution (40 g) and ion-exchanged water(1900 g) were simultaneously added dropwise over about two hours whilekeeping the temperature of the reaction vessel at 80° C. Furthermore,stirring was continued for about two hours while keeping the temperatureof the reaction vessel at 80° C. Thereafter, the temperature of thereaction vessel was cooled to room temperature and filtration wasperformed by a 100 mesh wire netting. The solid content concentrationwas controlled to be 10.0 mass % with ion-exchanged water to obtain awater dispersion of the polymer emulsion particle (HB-7) having a numberaverage particle size of 70 nm. The content of an aqueous-phasecomponent was 18 mass %.

Production Example 8 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-8)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (150 g),tetraethoxysilane (30 g), phenyltrimethoxysilane (145 g) and3-methacryloxypropyltrimethoxysilane (1.3 g) and a solution mixture ofdiethylacrylamide (150 g), (meth)acrylic acid ethylene glycol (15 g),acrylic acid (3 g), a reactive emulsifier (trade name “ADEKA REASOAPSR-1025”, manufactured by ADEKA Corporation, an aqueous solutioncontaining 25 mass % solid content) (13 g), a 2 mass % aqueous ammoniumpersulfate solution (40 g) and ion-exchanged water (1900 g) weresimultaneously added dropwise over about two hours while keeping thetemperature of the reaction vessel at 80° C. Furthermore, stirring wascontinued for about two hours while keeping the temperature of thereaction vessel at 80° C. Thereafter, the temperature of the reactionvessel was cooled to room temperature and filtration was performed by a100 mesh wire netting. The solid content concentration was controlled tobe 10.0 mass % with ion-exchanged water to obtain a water dispersion ofthe polymer emulsion particle (HB-7) having a number average particlesize of 70 nm. The content of an aqueous-phase component was 18 mass %.

Production Example 9 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-9)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of methyl methacrylate (150 g),tetraethoxysilane (30 g), phenyltrimethoxysilane (145 g) and3-methacryloxypropyltrimethoxysilane (1.3 g) and a solution mixture ofdiethylacrylamide (165 g), acrylic acid (3 g), a reactive emulsifier(trade name “ADEKA REASOAP SR-1025”, manufactured by ADEKA Corporation,an aqueous solution containing 25 mass % solid content) (13 g), a 2 mass% aqueous ammonium persulfate solution (40 g) and ion-exchanged water(1900 g) were simultaneously added dropwise over about two hours whilekeeping the temperature of the reaction vessel at 80° C. Furthermore,heat curing was continuously performed for about eight hours whilekeeping the temperature of the reaction vessel at 80° C. Thereafter, thetemperature of the reaction vessel was cooled to room temperature andfiltration was performed by a 100 mesh wire netting. The solid contentconcentration was controlled to be 10.0 mass % with ion-exchanged waterto obtain a water dispersion of the polymer emulsion particle (HB-9)having a number average particle size of 90 nm. The content of anaqueous-phase component was 5 mass %.

Production Example 10 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-10)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of cyclohexyl methacrylate (75g), methyl methacrylate (75 g), tetraethoxysilane (30 g),phenyltrimethoxysilane (145 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (165 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, heat curing was continuouslyperformed for about eight hours while keeping the temperature of thereaction vessel at 80° C. Thereafter, the temperature of the reactionvessel was cooled to room temperature and filtration was performed by a100 mesh wire netting. The solid content concentration was controlled tobe 10.0 mass % with ion-exchanged water to obtain a water dispersion ofthe polymer emulsion particle (HB-10) having a number average particlesize of 70 nm. The content of an aqueous-phase component was 5 mass %.

Production Example 11 Synthesis of Water Dispersion of Polymer EmulsionParticle (HB-11)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (6 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of cyclohexyl methacrylate (75g), methyl methacrylate (75 g), tetraethoxysilane (30 g),phenyltrimethoxysilane (145 g) and 3-methacryloxypropyltrimethoxysilane(1.3 g) and a solution mixture of diethylacrylamide (165 g), acrylicacid (3 g), a reactive emulsifier (trade name “ADEKA REASOAP SR-1025”,manufactured by ADEKA Corporation, an aqueous solution containing 25mass % solid content) (13 g), a 2 mass % aqueous ammonium persulfatesolution (40 g) and ion-exchanged water (1900 g) were simultaneouslyadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. Furthermore, heat curing was continuouslyperformed for about four hours while keeping the temperature of thereaction vessel at 80° C. Thereafter, the temperature of the reactionvessel was cooled to room temperature and filtration was performed by a100 mesh wire netting. The solid content concentration was controlled tobe 10.0 mass % with ion-exchanged water to obtain a water dispersion ofthe polymer emulsion particle (HB-11) having a number average particlesize of 70 nm. The content of an aqueous-phase component was 9 mass %.

Examples 1 to 35 Tables 1 to 4

“SNOWTEX” (component (A)) (trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %), apolymer emulsion particle (HB) obtained in each of Production Examplesand tetraethoxysilane (C) were blended in accordance with theformulations shown in Table 1. In this manner, coating compositions wereobtained. The particle sizes of “SNOWTEX” shown in the table were thoselisted in a catalog.

The obtained coating composition was applied onto a glass plate (5 cm×5cm) by dip coating, dried at 70° C. for 10 minutes to obtain a laminatehaving a coating film. The evaluation results of these are shown inTables 1 to 4.

TABLE 1 Examples (parts by mass) 1 2 3 4 5 6 7 Emulsion HB-1 Particlesize 70 nm particles HB-2 100 nm  HB-4 130 nm  HB-3 180 nm  HB-5 40 nmHB-6 20 nm HB-7 70 nm HB-8 70 nm HB-9 90 nm HB-10 70 nm 100 100 100 100100 100 100 HB-11 70 nm Content of aqueous- — 5 5 5 5 5 5 5 phasecomponent (%) Colloidal silica  8 nm 200 300 200 200 250 350 200 A(STOS) Colloidal silica 10 nm A (STO) Tetraethoxysilane C 107 (relativeto 100 g of component A) MS56C 120 80 160 120 120 10 (relative to 100 gof component A) Physical Optical Haze value 0.3 0.2 0.3 0.3 0.3 0.2 0.3properties of properties Total light 93.3 93.2 93.3 93.5 93.4 93.1 93.5coating film transmittance Refractive 1.42 1.43 1.42 1.44 1.43 1.41 1.44index Reflectivity 85.2 85.7 84.3 84.7 85 85.2 85.1 Film 500 500 500 500500 500 500 thickness (nm) Hydrophilicity Initial 6 5 4 4 4 6 7 (contactangle) After high- 11 13 15 13 11 12 13 temperature/ high-humidity testAfter high- 8 6 5 4 6 8 9 humidity test Heat — — — — — — — resistancetest Surface C/Si — — — — — 0.39 — composition Examples (parts by mass)8 9 10 11 12 13 Emulsion HB-1 Particle size 70 nm particles HB-2 100 nm HB-4 130 nm  HB-3 180 nm  HB-5 40 nm HB-6 20 nm HB-7 70 nm HB-8 70 nmHB-9 90 nm 100 100 100 HB-10 70 nm 100 100 100 HB-11 70 nm Content ofaqueous- — 5 5 5 5 5 5 phase component (%) Colloidal silica  8 nm 200200 200 300 400 400 A (STOS) Colloidal silica 10 nm A (STO)Tetraethoxysilane C 107 250 107 161 (relative to 100 g of component A)MS56C 27 54 (relative to 100 g of component A) Physical Optical Hazevalue 0.3 0.76 0.4 0.4 0.4 0.3 properties of properties Total light 93.493.6 — — 93.7 93.8 coating film transmittance Refractive 1.43 1.44 1.411.46 — — index Reflectivity 84.9 — — — — — Film 500 1000 — — 500 200thickness (nm) Hydrophilicity Initial 8 5 5 5 5 5 (contact angle) Afterhigh- 10 8 10 12 — — temperature/ high-humidity test After high- 8 6 6 76 6 humidity test Heat — — — — 25 29 resistance test Surface C/Si — — —— — — composition

TABLE 2 Examples (parts by mass) 14 15 16 17 18 19 20 21 Emulsion HB-1Particle size 70 nm 100 100 100 100 100 100 100 particles HB-2 100 nm HB-4 130 nm  HB-3 180 nm  HB-5 40 nm HB-6 20 nm HB-7 70 nm HB-8 70 nmHB-9 90 nm 100 HB-10 70 nm HB-11 70 nm Content of aqueous- — 5 18 18 1818 18 18 18 phase component (%) Colloidal silica Particle size  8 nm 200A (STOS) Colloidal silica 10 nm 120 115 120 250 300 350 300 A (STO)Tetraethoxysilane C 107 8.9 18 107 107 0.5 107 250 (relative to 100 g ofcomponent A) MS56C (relative to 100 g of component A) Physical OpticalHaze value 0.78 0.5 0.5 0.4 0.4 0.5 0.4 0.4 properties of propertiesTotal light 93.7 93.1 93.2 93.5 93.5 93.4 93.5 93.2 coating filmtransmittance Refractive 1.43 — — — — — — — index Reflectivity — — — — —— — — Film 1000 500 500 500 500 500 500 500 thickness (nm)Hydrophilicity Initial 5 7 10 8 11 6 11 12 (contact angle) After high- 9— — — — — — — temperature/ high-humidity test After high- 11 humiditytest Heat — 7 19 9 12 23 18 25 resistance test Surface C/Si 0.45 — — — —— — — composition Examples (parts by mass) 22 23 24 25 26 27 28 EmulsionHB-1 Particle size 70 nm particles HB-2 100 nm  HB-4 130 nm  HB-3 180nm  HB-5 40 nm 100 HB-6 20 nm 100 HB-7 70 nm 100 100 100 HB-8 70 nm 100HB-9 90 nm HB-10 70 nm HB-11 70 nm 100 Content of aqueous- — 9 18 18 1818 18 18 phase component (%) Colloidal silica Particle size  8 nm 200 A(STOS) Colloidal silica 10 nm 200 200 200 100 200 200 A (STO)Tetraethoxysilane C 107 107 107 10 50 107 (relative to 100 g ofcomponent A) MS56C 54 (relative to 100 g of component A) PhysicalOptical Haze value 0.3 0.3 0.2 0.4 0.5 0.4 0.4 properties of propertiesTotal light 93.6 93.1 92.9 93.4 93.6 93.5 93.5 coating filmtransmittance Refractive 1.43 1.44 1.45 1.41 1.39 1.4 1.4 indexReflectivity — — — — — — — Film 500 500 500 500 500 500 500 thickness(nm) Hydrophilicity Initial 7 12 15 8 13 10 9 (contact angle) Afterhigh- 15 — — — — — — temperature/ high-humidity test After high- 9 15 1814 17 13 12 humidity test Heat 8 20 23 17 20 19 19 resistance testSurface C/Si 0.47 — — — — — — composition

TABLE 3 Example Example Example Example (parts by mass) 29 30 31 32Emulsion HB-1 70 nm 100 particles HB-2 100 nm  100 100 HB-4 130 nm  100HB-3 180 nm  HB-5 40 nm HB-6 20 nm HB-7 70 nm HB-8 70 nm HB-9 90 nmHB-10 70 nm HB-11 70 nm Content of aqueous- — 18 18 18 18 phasecomponent (%) Colloidal silica Particle size  8 nm 100 100 A (STOS)Colloidal silica Particle size 10 nm 100 100 A (STO) Tetraethoxysilane C69 0 8.9 0.8 (relative to 100 g of component A) MS56C (relative to 100 gof component A) Physical Optical Haze value 1 1.5 0.5 1.1 properties ofproperties Total light 93.5 93.6 93.5 93.5 coating film transmittanceRefractive 1.4 1.38 — — index Reflectivity — — — — Film 500 500 500 500thickness (nm) Appearance ◯ ◯ ◯ ◯ Hydrophilicity Initial 12 15 13 12(contact angle) After high- 55 75 — — temperature/ high-humidity testAfter high- 42 45 38 39 humidity test Heat 38 40 38 40 resistance testSurface C/Si 0.68 0.72 0.58 — composition

TABLE 4 Example Example Example (parts by mass) 33 34 35 Emulsion HB-170 nm 100 particles HB-2 100 nm  HB-4 130 nm  100 HB-3 180 nm  100 HB-540 nm HB-6 20 nm HB-7 70 nm HB-8 70 nm HB-9 90 nm HB-10 70 nm HB-11 70nm Content of aqueous-phase component (%) — 18 18 18 Colloidal silica A(STOS)  8 nm Colloidal silica A (STO) 10 nm 500 100 100Tetraethoxysilane C (relative to 143 8.9 8.9 100 g of component A) MS56C(relative to 100 g of component A) Titanium oxide (A2) Physical OpticalHaze value 2 1.2 1.5 properties of properties Total light 92.5 92.6 92.6coating film transmittance Refractive — — — index Reflectivity — — —Film 200 500 500 thickness (nm) Appearance ◯ ◯ ◯ Hydrophilicity Initial10 12 11 (contact angle) After high- — — — temperature/ high-humiditytest After high- 35 37 37 humidity test Heat 34 36 38 resistance testSurface C/Si — — — composition

As is apparent from Tables 1 to 4, it was demonstrated that thelaminates of Examples are excellent at least in transparency andhydrophilicity and maintain surface hydrophilicity even at hightemperature and the like.

(Study on Antistatic Use; Table 5)

“SNOWTEX O” (component (A))(trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %, a numberaverage particle size: 10 nm), a polymer emulsion particle (HB) obtainedin each of Production Examples and tetraethoxysilane (C) were blended asshown in Table 5 to obtain an antistatic coating composition.Subsequently, the obtained coating composition was applied onto a glassplate (5 cm×5 cm) by dip coating and then dried at 70° C. for 10 minutesto obtain an antistatic composite. The evaluation results of these areshown in Table 5.

TABLE 5 Comparative Examples Example (parts by mass) 36 37 1 SubstratePC PC PC HB-1 Particle size 70 nm 100 — — HB-2 Particle size 100 nm  —100  — Content of aqueous-phase (%)  18 18 — component Colloidal silicaA Particle size 10 nm 200 100  — Tetraethoxysilane C 107   8.9 —(relative to 100 g of component A) Antistatic composite Physical Initialcontact  7 12 78 properties angle Initial haze value    0.4   1.1   0.4Appearance ◯ ◯ ◯ Surface resistance   10¹¹  10¹³  10¹⁵ value (Ω) PC:Polycarbonate resin

As shown in Table 5, it was demonstrated that the composites of Examplesare excellent at least in hydrophilicity, transparency, appearance andsurface resistance value.

(Study on Antireflection Use; Table 6)

“SNOWTEX O” (component (A)) (trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %, a numberaverage particle size: 10 nm), a polymer emulsion particle (HB) obtainedin each of Production Examples and tetraethoxysilane (C) were blended asshown in Table 6 to obtain an antireflection coating composition.Subsequently, the obtained coating composition was applied onto a glassplate (5 cm×5 cm) by dip coating and then dried at 70° C. for 10 minutesto obtain an antireflection composite. The evaluation results of theseare shown in Table 6.

TABLE 6 Examples (parts by mass) 38 39 40 41 42 Substrate Glass GlassGlass Glass Glass HB-1 Particle size 130 nm 100 — — — — HB-2 Particlesize 100 nm — — — 100 100 HB-3 Particle size 180 nm — 100 100 — —Content of aqueous- (%) 18 18 18 18 18 phase component Colloidal silicaA Particle size  10 nm 100 200 300 20 200 Tetraethoxysilane C 8.9 8.9107 0 69 (relative to 100 g of component A) Antireflection Initialphysical Initial contact angle 8 8 11 28 12 composite properties Initialhaze value 1.1 1.8 1.6 1.8 1.1 Appearance ◯ ◯ ◯ ◯ ◯ Reflectivity 2.80%3.2% 3.30% 4.10% 4.80%

As shown in Table 6, it was demonstrated that the composites of Examplesare excellent at least in hydrophilicity, transparency, appearance andreflectivity.

(Study on Hard Coating Use; Table 7)

“SNOWTEX O” (component (A))(trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %, a numberaverage particle size: 10 nm), a polymer emulsion particle (HB) obtainedin each of Production Examples and tetraethoxysilane (C) were blended asshown in Table 7 to obtain a coating composition for hard coating.Subsequently, the obtained coating composition was applied onto apolycarbonate (PC) plate (5 cm×5 cm) of 3 mm in thickness by dip coatingand then dried at 70° C. for 10 minutes to obtain a hard coatingcomposite. The evaluation results of these are shown in Table 7.

TABLE 7 Comparative Examples Example (parts by mass) 43 44 45 46 2Substrate PC PC PC PC PC HB-1 Particle size  70 nm 100 100 — — — HB-2Particle size 100 nm — — 100 — — HB-3 Particle size 180 nm — — — 100 —Content of aqueous- (%) 18 — — — — phase component Colloidal silica AParticle size  10 nm 150 300 20 380 — Tetraethoxysilane C 8.9 8.9 0 0 —(relative to 100 g of component A) Hard coating Initial physical Initialcontact angle 8 8 28 10 78 composite properties Initial haze value 0.40.5 1.1 1.5 0.4 Appearance ◯ ◯ ◯ ◯ ◯ Abrasion resistance ◯ ◯ Δ X XPencil hardness 3H 2H H F F PC: Polycarbonate resin

As shown in Table 7, it was demonstrated that the composites of Examplesare excellent at least in hydrophilicity, transparency, appearance andpencil hardness. Furthermore, it was demonstrated that composites ofExamples 43 to 45 have abrasion resistance as excellent as practicallevel.

(Study on Solvent Resistant Use; Table 8)

“SNOWTEX O” (component (A)) (trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %, a numberaverage particle size: 10 nm), a polymer emulsion particle (HB) obtainedin each of Production Examples and tetraethoxysilane (C) were blended asshown in Table 8 to obtain a solvent resistant coating composition.Subsequently, the obtained coating composition was applied onto apolycarbonate plate (5 cm×5 cm) by dip coating and then dried at 70° C.for 10 minutes to obtain a solvent resistant composite. The evaluationresults of these are shown in Table 8.

TABLE 8 Comparative Examples Example (parts by mass) 47 48 49 3Substrate PC PC PC PC HB-1 Particle size 70 nm 100 — 100 — HB-2 Particlesize 100 nm  — 100 — — Content of aqueous- (%) 18 — — — phase componentColloidal silica A Particle size 10 nm 120 20 500 — Tetraethoxysilane C8.9 0 8.9 — (relative to 100 g of component A) Solvent resistantPhysical Initial contact angle 7 28 10 78 composite properties Initialhaze value 0.5 1.1 0.8 0.4 Appearance ◯ ◯ X — Appearance after solvent ◯Δ — X resistance test

As shown in Table 8, it was demonstrated that the composites of Examplesare excellent at least in hydrophilicity and transparency. Furthermore,it was demonstrated that the composites of Examples 47 and 48 haveappearance (after the solvent resistance test) as excellent as practicallevel.

(Study on Heat Resistant Use; Table 9)

“SNOWTEX O” (component (A)) (trade name, manufactured by Nissan ChemicalIndustries, Ltd.) dispersed in water (solid content: 10 mass %, a numberaverage particle size: 10 nm), a polymer emulsion particle (HB) obtainedin each of Production Examples and tetraethoxysilane (C) were blended asshown in Table 9 to obtain a heat resistant coating composition.Subsequently, the obtained coating composition was applied onto a glassplate (5 cm×5 cm) by dip coating and then dried at 70° C. for 10 minutesto obtain a heat resistant composite. The evaluation results of theseare shown in Table 9.

TABLE 9 Comparative Examples Example (parts by mass) 50 51 52 53 4Substrate PC PC PC PC PC HB-1 Particle size 70 nm 100 100 — — — HB-2Particle size 100 nm  — — 100 100 — Content of aqueous- (%) 18 18 18 18— phase component Colloidal silica A Particle size 10 nm 150 300 20 300— Tetraethoxysilane C 20 20 0 0.9 — (relative to 100 g of component A)Heat resistant Physical Initial contact angle 6 5 28 10 78 compositeproperties Initial haze value 0.4 0.4 1.1 0.8 0.4 Appearance ◯ ◯ ◯ ◯ ◯Appearance after heat ◯ ◯ Δ Δ X resistance test Haze value after heat0.5 0.5 2.1 2.2 24 resistance test PC: Polycarbonate resin

As shown in Table 9, it was demonstrated that the composites of Examplesare excellent at least in hydrophilicity, transparency, appearance afterheat resistance test and transparency after heat resistance test. Inparticular, it was demonstrated that the composites of Examples 50 and51 have more excellent appearance after the heat resistance test.

Study on Functional Composite; Table 10 Example 54

Colloidal silica (trade name “SNOWTEX O” (A), manufactured by NissanChemical Industries, Ltd., dispersed in water, solid content: 10 mass %,a number average particle size: 10 nm), polymer emulsion particles(HB-1) and (HB-2) obtained in each of Production Examples andtetraethoxysilane (C) were blended at a ratio shown in Table 10 toobtain a coating composition.

The obtained coating composition was applied onto a substrate (5 cm×5cm) formed of polycarbonate resin and having a thickness of 3 mm by dipcoating and then dried at 70° C. for 10 minutes to obtain a coatingfilm. Furthermore, a heat treatment and a pressurization treatment wereapplied to the coating film by use of LM50 vacuum laminate apparatus(manufactured by NPC) in condition 1 (degassed at 150° C. for 5 minutes,subjected to a vacuum lamination process for 10 minutes at a pressure of100 kPa) to obtain a functional composite. The evaluation results areshown in Table 10.

Examples 55 and 56

A coating composition was obtained in the same manner as in Example 54except that the composition was changed as shown in Table 10. Theobtained coating composition was applied onto a substrate (5 cm×5 cm)formed of polycarbonate resin and having a thickness of 3 mm by dipcoating and then dried at 70° C. for 10 minutes to obtain a coatingfilm. Furthermore, a heat treatment was applied to the coating film incondition 2 (heating in air, at 150° C. for 30 minutes) in place ofcondition 1 to obtain a functional composite. The evaluation results areshown in Table 10.

Comparative Example 5

Only a polycarbonate resin serving as a substrate was used. Evaluationwas performed in the same manner as in Example 1 except that thecomposition was changed as shown in Table 10. The evaluation results areshown in Table 10.

TABLE 10 Comparative Examples Example (parts by mass) 54 55 56 5Substrate PC PC PC PC HB-1 Particle size 70 nm 100 100 100 — Colloidalsilica A Particle size 10 nm 150 150 150 — Content of aqueous- (%) 18 1818 — phase component Tetraethoxysilane C 12 12 12 — (relative to 100 gof component A) Post-treatment condition 1 2 None None FunctionalPhysical Initial contact angle 12 12 6 78 composite properties Initialhaze value 0.4 0.4 0.4 0.4 Appearance ◯ ◯ ◯ — Appearance after solvent ⊚◯ Δ X resistance test Surface hardness 2H H HB F

As shown in Table 10, it was demonstrated that the composites ofExamples are excellent at least in hydrophilicity, transparency,appearance after solvent resistance test and surface hardness.

Laminate Production; Table 11 Example 57

Colloidal silica (trade name “SNOWTEX-OS” (component (A)) manufacturedby Nissan Chemical Industries, Ltd.) was diluted with water to prepare afluid dispersion having a 10 mass % solid content (number averageparticle size of 8 nm). To this, a water dispersion of each of polymeremulsion particles synthesized in Production Examples, was blended andcomponent (C):

tetraethoxysilane (trade name “KBE-04” manufactured by Shin-EtsuChemical Co., Ltd.) was blended so as to satisfy the composition shownin Table 11, and balanced with pure water such that the total solidcontent was 4 mass % to obtain a coating composition.

The resultant coating composition was applied onto the surface of glasssurface of a reflecting mirror (formed by plating with aluminum on therear (lower) surface of a glass plate) by dip coating so as to obtain apredetermined thickness after drying. Subsequently, the dip coatedmirror was dried at 70° C. for 30 minutes to obtain a laminate.

Note that a laminate was prepared in the same manner as above exceptthat the substrate was changed from a reflecting mirror to a white crownglass plate (thickness 2 mm, 6×6 cm squares) and subjected tomeasurement of haze.

Example 58

A laminate was prepared in the same manner as in Example 57 by using acoating composition blended in the same manner as in Example 57 exceptthat the thickness of a coating film was changed as shown in Table 11.Furthermore, a coating composition was applied onto the coating film ofthe laminate by dip coating and dried at 70° C. for 30 minutes to obtaina laminate having a plurality of coating film layers.

Example 59

A laminate was prepared in the same manner as in Example 57 by using acoating composition blended in the same manner as in Example 57 exceptthat the composition was changed to that shown in Table 11 except thatthe thickness of the coating film was changed to that shown in Table 11.

Example 60

A laminate was prepared in the same manner as in Example 59 by using acoating composition blended in the same manner as in Example 59 exceptthat the thickness of the coating film was changed as shown in Table 11.Subsequently, the surface of the coating film was rubbed 100 times bysandpaper (#1000) with the application of a load of 22 g/cm².Thereafter, on the coating film having a rubbed surface, a coatingcomposition was applied by dip coating and dried at 70° C. for 30minutes to obtain a laminate having a plurality of coating film layers.

Comparative Example 6

A reflecting mirror alone serving as a substrate was used.

Evaluation results of Examples and Comparative Examples are shown inTable 11.

TABLE 11 Comparative Examples Example 57 58 59 60 6 Refractive index ofsubstrate 1.51 1.51 1.51 1.51 1.51 Coating Colloidal silica A (Particlesize: 8 nm) 200 200 200 200 — film HB-9 (Particle size: 90 nm) 100 100100 100 — Content of aqueous-phase component (%) 5 5 5 5 —Tetraethoxysilane C 107 107 160 160 — (relative to 100 g of component A)First layer from Thickness (nm) 252 245 250 245 — substrate sideRefractive index 1.44 1.44 1.47 1.47 — Second layer from Thickness (nm)— 230 — 240 — substrate side Refractive index — 1.44 — 1.47 — Totalthickness of coating film (nm) 252 475 250 485 — Difference inrefractive index between coating 0.07 0.07 0.04 0.04 — film andsubstrate Physical Contact angle 6 7 5 6 38 properties Reflectivity 90.590.6 90.9 90.8 90.8 Haze value 0.6 0.5 0.4 0.5 — Appearance ◯ ◯ ◯ ◯ —

As shown in Table 11, it was demonstrated that the laminates of Examplesare excellent at least in hydrophilicity, reflectivity, transparency andappearance.

Study on Laminate, Transmittance; Tables 12, 13 Example 61

“SNOWTEX OS” (component (A)) (trade name, manufactured by NissanChemical Industries, Ltd.) was diluted with water to prepare a fluiddispersion (solid content: 10 mass %, number average particle size: 8nm). To this, the polymer emulsion (HB1) synthesized in ProductionExample 1 was blended and tetraethoxysilane (C) (trade name “KBE-04”manufactured by Shin-Etsu Chemical Co., Ltd.) was blended in accordancewith the composition shown in Table 12 to obtain a coating composition.

The obtained coating composition was applied by spin coating onto awhite crown glass plate (thickness: 2 mm, 6×6 cm squares) so as toobtain a film thickness of 250 nm and dried at 70° C. for 30 minutes toobtain a laminate.

Example 62

A laminate was formed using the coating composition so as to satisfy thecomposition described in Table 12 in the same manner as in Example 61.Thereafter, the coating composition was applied in the same manner toform a layer on the laminate. In this manner, a multi-layer laminate wasobtained.

Example 63

A laminate was obtained in the same manner as in Example 61 except thata coating liquid was prepared in accordance with the formulation shownin Table 12.

Example 64

A layer was repeatedly formed on the laminate in the same procedure asin Example 61 to obtain a laminate having 10 layers formed of thecoating composition.

Example 65

After a single layer formed of the coating composition was stacked inthe same manner as in Example 61, a surface of the coating film wasrubbed 10 times by steel wool (#7448) with the application of a load of22 g/cm². Thereafter, a single layer formed of the coating compositionwas again stacked to obtain a laminate.

Example 66

A laminate was obtained in the same manner as in Example 61 except thata substrate was changed to a polycarbonate resin named “IUpilon”(thickness: 3 mm, 5×5 cm squares) manufactured by MitsubishiEngineering-Plastics Corporation.

Comparative Example 7

The evaluation results of only a white crown glass plate serving as asubstrate are shown in Table 13.

Comparative Example 8

The evaluation results of only a polycarbonate resin serving as asubstrate are shown in Table 13.

Comparative Example 9

“SNOWTEX OS” (component (A)) (trade name, manufactured by NissanChemical Industries, Ltd.) was diluted with water to prepare a fluiddispersion (solid content: 10 mass %, number average particle size: 8nm). To this, a polymer emulsion synthesized in a Production Example wasblended in accordance with the composition shown in Table 13 and 30parts of methyltrimethoxysilane (C) (trade name “KBM-13” manufactured byShin-Etsu Chemical Co., Ltd.) were added to obtain a coatingcomposition.

The resultant coating composition was applied onto a white crown glassplate (thickness: 2 mm, 6×6 cm squares) so as to obtain a film thicknessof 250 nm by spin coating and then dried at 70° C. for 30 minutes toobtain a laminate.

Comparative Example 10

Coating was further repeated onto the laminate obtained in ComparativeExample 9 in the same manner. However, a two-layer laminate was notobtained since a coating liquid was repelled.

Evaluation results of Examples and Comparative Examples are shown inTables 12 and 13.

TABLE 12 Examples (parts by mass) 61 62 63 64 65 66 Substrate (*) GlassGlass Glass Glass Glass PC Coating Refractive index 1.51 1.51 1.51 1.511.51 1.58 film Colloidal silica A Particle size  8 nm 200 200 200 200200 200 HB-1 Particle size 70 nm 100 100 100 100 100 100 Content ofaqueous- (%) 18 18 18 18 18 18 phase component Tetraethoxysilane C 0 0107 107 107 107 (relative to 100 g of component A) First layer Filmthickness nm 220 220 250 250 250 280 Refractive index 1.41 1.41 1.391.39 1.39 1.39 Second layer Film thickness nm — 220 250 250 250 300Refractive index — 1.41 1.39 1.39 1.39 1.39 Tenth layer Film thicknessnm — — — 250 — — Refractive index — — — 1.39 — — Total film thickness nm220 440 500 2500 500 580 Difference in 0.1 0.1 0.12 0.12 0.12 0.19refractive index Physical Contact angle 5.2 5 3.9 8.5 5 14.8 propertiesTotal light transmittance 92.84 93.14 94.08 93.36 93.73 90.24 Haze value0.2 0.18 0.23 0.85 0.66 1.49 Appearance ◯ ◯ ◯ ◯ ◯ ◯ (*) Glass: whitecrown glass, PC: polycarbonate

TABLE 13 Comparative Example (parts by mass) 7 8 9 10 Substrate (*)Glass PC Glass Glass Coating Refractive index 1.51 1.58 1.51 1.51 filmColloidal silica A Particle size  8 nm — — 200 200 HB-1 Particle size 70nm — — 0 0 Content of aqueous- (%) — — — — phase componentTetraethoxysilane C — — 240 240 (relative to 100 g of component A) Firstlayer Film thickness nm — — 300 300 Refractive index — — 1.44 1.44Second layer Film thickness nm — — — — Refractive index — — — — Tenthlayer Film thickness nm — — — — Refractive index — — — — Total filmthickness nm — — 300 — Difference in — — 0.07 — refractive indexPhysical Contact angle 35 80 73 — properties Total light transmittance92.51 89.23 93.93 — Haze value 0.12 0.51 0.07 — Appearance — — ◯ X (*)Glass: white crown glass, PC: polycarbonate

As shown in Tables 12 and 13, it was demonstrated that the laminates ofExamples are excellent at least in hydrophilicity, transparency andappearance. In contrast, it was demonstrated that the laminates ofComparative Examples are inferior in at least one of hydrophilicity,transparency and appearance.

Study on Aqueous Coating Composition (Titanium Oxide used incombination); Table 14 Examples 67 to 69

Colloidal silica (trade name “SNOWTEX-OS” (component (A)) manufacturedby Nissan Chemical Industries, Ltd.) was diluted with water to prepare afluid dispersion having a 10 mass % solid content (a number averageparticle size of 8 nm). To this, a photocatalyst (trade name “TSK-5”manufactured by Ishihara Sangyo Kaisha, Ltd., a number average particlesize: 10 nm, silica coated titanium oxide hydro sol) (component (A3))and a water dispersion of a polymer emulsion particle synthesized in aProduction Example were blended in accordance with the composition shownin Table 14 to obtain a coating composition. The obtained coatingcomposition was applied onto a white crown glass plate (thickness: 2 mm,6×6 cm squares) by spin coating so as to obtain a film thickness of 250nm and dried at 70° C. for 30 minutes to obtain a laminate consisting ofthe white crown glass plate serving as a substrate and a coating filmformed thereon.

Examples 70 and 71

A coating composition was obtained in the same manner as in Example 67except that tetraethoxysilane (trade name “KBE-04” manufactured byShin-Etsu Chemical Co., Ltd.) was further added as a component (C) inaccordance with the composition shown in Table 14. A laminate wasobtained in the same manner as in Example 67 except that the coatingcomposition was used.

Example 72

A coating composition was obtained in the same manner as in Example 67except that blending was made so as to obtain the composition describedin Table 14. A laminate was obtained in the same manner as in Example 67except that the coating composition was used.

The results of Examples and Comparative Examples are shown in Table 14.

TABLE 14 Examples (parts by mass) 67 68 69 Colloidal silica A1 Particle8 nm 100 200 200 size Titanium oxide sol A3 Particle 10~30 nm 5 5 10size HB-1 Particle 70 nm 100 100 100 size Content of low-molecular (%)18 18 18 weight substance Tetraethoxysilane C 0 0 0 (relative to 100 gof component A) A1/(A1 + A3) Mass ratio 95.3/100 97.6/100 95.3/100 C/A1Mass ratio   0/100   0/100   0/100 Initial Contact angle 12 7 8 Hazevalue 0.67 0.33 0.4 Refractive index 1.4 1.4 1.43 After weatherresistance test Contact angle 15 10 8 After heating test Contact angle30 25 20 Examples (parts by mass) 70 71 72 Colloidal silica A1 Particle8 nm 200 200 100 size Titanium oxide sol A3 Particle 10~30 nm 3 5 0 sizeHB-1 Particle 70 nm 100 100 100 size Content of low-molecular (%) 18 1818 weight substance Tetraethoxysilane C 107 107 0 (relative to 100 g ofcomponent A) A1/(A1 + A3) Mass ratio 98.5/100 97.6/100   0/100 C/A1 Massratio   50/100   50/100   0/100 Initial Contact angle 7 6 13 Haze value0.6 0.65 0.5 Refractive index 1.46 1.47 1.39 After weather resistancetest Contact angle 7 5 22 After heating test Contact angle 18 17 38

As shown in Table 14, it was demonstrated that the laminates of Examplesare excellent at least in initial hydrophilicity, transparency andrefractive index; at the same time, excellent in hydrophilicity afterthe weather resistance test and the heating test.

Study on Functional Coating Film; Table 15 Example 73

“SNOWTEX-OS” (component (A)) (trade name manufactured by Nissan ChemicalIndustries, Ltd.) was diluted with water to prepare a fluid dispersionhaving a 10 mass % solid content (number average particle size of 8 nm).To this, a polymer emulsion synthesized in a Production Example wasblended in accordance with the formulation shown in Table 15 to obtain acoating composition.

The obtained coating composition was applied onto a white crown glassplate (thickness: 2 mm, 6×6 cm squares) by spin coating so as to obtaina film thickness of 250 nm and dried at 70° C. for 30 minutes to obtaina functional coating film.

Example 74

A functional coating film was obtained in the same manner as in Example74 except that a coating composition was obtained in accordance with theformulation shown in Table 15.

Example 75

A functional coating film was obtained in the same manner as in Example74 except that a coating composition was obtained in accordance with theformulation shown in Table 15.

Example 76

“SNOWTEX-OS” (component (A)) (trade name manufactured by Nissan ChemicalIndustries, Ltd.) was diluted with water to prepare a fluid dispersionhaving a 10 mass % solid content (number average particle size of 8 nm).To this, a polymer emulsion synthesized in a Production Example wasblended and tetraethoxysilane (C) (trade name “KBE-04” manufactured byShin-Etsu Chemical Co., Ltd.) was blended in accordance with theformulation shown in Table 15 to obtain a coating composition.

The obtained coating composition was applied onto a white crown glassplate (thickness: 2 mm, 6×6 cm squares) by spin coating so as to obtaina film thickness of 250 nm and dried at 70° C. for 30 minutes to obtaina functional coating film.

Example 77

A functional coating film was obtained in the same manner as in Example74 except that a coating composition was obtained in accordance with theformulation shown in Table 15.

Example 78

A functional coating film was obtained in the same manner as in Example74 except that a coating composition was obtained in accordance with theformulation shown in Table 15.

Comparative Example 11

Evaluation was made by using only a glass plate serving as a substrate.

TABLE 15 Examples (parts by mass) 73 74 75 76 Colloidal silica AParticle size  8 nm 100 100 200 200 HB-2 Particle size 100 nm  10 0 0 0HB-1 Particle size 70 nm 0 100 100 100 Content of aqueous- (%) 18 18 1818 phase component Tetraethoxysilane C 0 0 0 160 (relative to 100 g ofcomponent A) Functional coating film Film thickness nm 500 500 500 500Refractive index 1.35 1.37 1.4 1.41 Physical properties Contact angle °4.8 20 5.2 3.9 Total light % 94.5 94.3 93.9 94.1 transmittance Circleequivalent nm 30 80 200 300 diameter Porosity % 60 29 13 36 ComparativeExamples Example (parts by mass) 77 78 11 Colloidal silica A Particlesize  8 nm 200 50 — HB-2 Particle size 100 nm  0 0 — HB-1 Particle size70 nm 100 100 — Content of aqueous- (%) 18 18 phase componentTetraethoxysilane C 107 0 — (relative to 100 g of component A)Functional coating film Film thickness nm 500 500 0 Refractive index1.39 1.49 1.51 Physical properties Contact angle ° 5.9 60 40 Total light% 93.7 92.7 92.5 transmittance Circle equivalent nm 300 5 — diameterPorosity % 17 2 —

As shown in Table 15, it was demonstrated that the laminates of Examplesare excellent in refractive index, transparency and appearance.

Production Example 12 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-1)

To a reaction vessel having a reflux condenser, a dropping tank, athermometer and a stirrer, ion-exchanged water (1600 g) and dodecylbenzene sulfonic acid (4 g) were supplied, and heated to increase thetemperature to 80° C. under stirring. To this, a solution mixture ofdimethyldimethoxysilane (185 g) and phenyltrimethoxysilane (117 g) wasadded dropwise over about two hours while keeping the temperature of thereaction vessel at 80° C. and thereafter stirring was continued forabout one hour while keeping the temperature of the reaction vessel at80° C. Subsequently, a solution mixture of butyl acrylate (150 g),tetraethoxysilane (30 g), phenyltrimethoxysilane (145 g) and3-methacryloxypropyltrimethoxysilane (1.3 g) and a solution mixture ofdiethylacrylamide (165 g), acrylic acid (3 g), a reactive emulsifier(trade name “ADEKA REASOAP SR-1025”, manufactured by ADEKA Corporation,an aqueous solution containing 25 mass % solid content) (13 g), a 2 mass% aqueous ammonium persulfate solution (40 g) and ion-exchanged water(1900 g) were simultaneously added dropwise over about two hours whilekeeping the temperature of the reaction vessel at 80° C. Furthermore, asheat curing stirring was subsequently performed for about 15 hours whilekeeping the temperature of the reaction vessel at 80° C. Thereafter, thetemperature of the reaction vessel was cooled to room temperature andfiltration was performed by a 100 mesh wire netting to obtain a waterdispersion of the polymer emulsion particle (TB-1) having a solidcontent of 14.03 mass %, an aqueous-phase component of 2.76 mass % andhaving a number average particle size of 131 nm.

The water dispersion of the polymer emulsion particle (TB-1) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-1) containing the aqueous-phase component. The obtained filtrate(H-1) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-1). A deionized water drop was placed on the film surface ofthe test plate (I-1) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 57°.

Production Example 13 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-2)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 8 hours to obtain a water dispersion of the polymer emulsion particle(TB-2) having a solid content of 14.05 mass %, an aqueous-phasecomponent of 4.57 mass % and a number average particle size of 132 nm.

The water dispersion of the polymer emulsion particle (TB-2) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-2) containing the aqueous-phase component. The obtained filtrate(H-2) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-2). A deionized water drop was placed on the film surface ofthe test plate (I-2) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 56°.

Production Example 14 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-3)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 4 hours to obtain a water dispersion of the polymer emulsion particle(TB-3) having a solid content of 14.08 mass %, an aqueous-phasecomponent of 8.91 mass % and a number average particle size of 131 nm.

The water dispersion of the polymer emulsion particle (TB-3) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-3) containing the aqueous-phase component. The obtained filtrate(H-3) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-3). A deionized water drop was placed on the film surface ofthe test plate (I-3) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 58°.

Production Example 15

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 3.5 hours to obtain a water dispersion of a polymer emulsion particle(TB-4) having a solid content of 14.02 mass %, an aqueous-phasecomponent of 11.46 mass % and a number average particle size of 131 nm.

The water dispersion of the polymer emulsion particle (B-4) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-4) containing the aqueous-phase component. The obtained filtrate(H-4) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-4). A deionized water drop was placed on the film surface ofthe test plate (I-4) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 57°.

Production Example 16 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-5)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 3 hours to obtain a water dispersion of the polymer emulsion particle(TB-5) having a solid content of 14.05 mass %, an aqueous-phasecomponent of 14.12 mass % and a number average particle size of 130 nm.

The water dispersion of the polymer emulsion particle (TB-5) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-5) containing the aqueous-phase component. The obtained filtrate(H-5) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-5). A deionized water drop was placed on the film surface ofthe test plate (I-5) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 57°.

Production Example 17

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 2.5 hours to obtain a water dispersion of the polymer emulsionparticle (TB-6) having a solid content of 14.07 mass %, an aqueous-phasecomponent of 16.34 mass % and a number average particle size of 130 nm.

The water dispersion of the polymer emulsion particle (B-6) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-6) containing the aqueous-phase component. The obtained filtrate(H-6) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-6). A deionized water drop was placed on the film surface ofthe test plate (I-6) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 58°.

Production Example 18 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-7)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe 2 hours to obtain a water dispersion of the polymer emulsion particle(TB-7) having a solid content of 14.06 mass %, an aqueous-phasecomponent of 18.19 mass % and a number average particle size of 129 nm.

The water dispersion of the polymer emulsion particle (TB-7) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-7) containing the aqueous-phase component. The obtained filtrate(H-7) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-7). A deionized water drop was placed on the film surface ofthe test plate (I-7) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 57°.

Production Example 19 Synthesis of Water Dispersion of Polymer Emulsionparticle (TB-8)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing time described in Production Example 12 was set tobe one hour to obtain a water dispersion of the polymer emulsionparticle (TB-8) having a solid content of 14.09 mass %, an aqueous-phasecomponent of 21.93 mass % and a number average particle size of 130 nm.

The water dispersion of the polymer emulsion particle (TB-8) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-8) containing the aqueous-phase component. The obtained filtrate(H-8) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-8). A deionized water drop was placed on the film surface ofthe test plate (I-8) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 56°.

Production Example 20 Synthesis of Water Dispersion of Polymer EmulsionParticle (TB-9)

Polymerization was performed in the same method as in Synthesis Example1 and the heat curing described in Production Example 12 was notperformed to obtain a water dispersion of the polymer emulsion particle(TB-9) having a solid content of 14.11 mass %, an aqueous-phasecomponent of 28.66 mass % and a number average particle size of 128 nm.

The water dispersion of the polymer emulsion particle (TB-8) wasfiltrated by use of an ultrafiltration apparatus to obtain a filtrate(H-8) containing the aqueous-phase component. The obtained filtrate(H-8) was applied onto a soda lime glass plate (5×5 cm squares) by dipcoating and then dried at 90° C. for 24 hours to obtain a film-form testplate (I-8). A deionized water drop was placed on the film surface ofthe test plate (I-8) thus obtained and allowed to stand still at 20° C.for 10 seconds. The initial contact angle as then measured was 58°.

Example 79

To the water dispersion of the polymer emulsion particle (TB-1) (100 g)synthesized in Production Example 12, 100 g of water-dispersed colloidalsilica (trade name “SNOWTEX O”, manufactured by Nissan ChemicalIndustries, Ltd., solid content: 20 mass %) having a number averageparticle size of 12 nm was blended and stirred to obtain an aqueousorganic/inorganic composite composition (E-1).

The aqueous organic/inorganic composite composition (E-1) was appliedonto a soda lime glass plate (5×5 cm squares) by bar coating so as toobtain a film thickness of 1 μm and thereafter dried at 70° C. for 30minutes to obtain a test plate (G-1) having an organic/inorganiccomposite film (F-1). The initial contact angle of the obtained testplate (G-1) having an organic/inorganic composite film with water was7.2°.

Example 80

A test plate (G-2) having an organic/inorganic composite film (F-2) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-2) synthesized inProduction Example 13 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-2)having an organic/inorganic composite film with water was 7.2°.

Example 81

A test plate (G-3) having an organic/inorganic composite film (F-3) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-3) synthesized inProduction Example 14 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-3)having an organic/inorganic composite film with water was 7.2°.

Example 82

A test plate (G-4) having an organic/inorganic composite film (F-4) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-4) synthesized inProduction Example 15 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-4)having an organic/inorganic composite film with water was 7.2°.

Example 83

A test plate (G-5) having an organic/inorganic composite film (F-5) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-5) synthesized inProduction Example 16 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-5)having an organic/inorganic composite film with water was 7.2°.

Example 84

A test plate (G-6) having an organic/inorganic composite film (F-6) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-6) synthesized inProduction Example 17 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-6)having an organic/inorganic composite film with water was 7.2°.

Example 85

A test plate (G-7) having an organic/inorganic composite film (F-7) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-7) synthesized inProduction Example 18 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-7)having an organic/inorganic composite film with water was 7.2°.

Comparative Example 12

A test plate (G-8) having an organic/inorganic composite film (F-8) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-8) synthesized inProduction Example 19 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-8)having an organic/inorganic composite film with water was 7.2°.

Comparative Example 13

A test plate (G-9) having an organic/inorganic composite film (F-9) wasobtained by the same method as in Example 79 except that the waterdispersion of the polymer emulsion particle (TB-9) synthesized inProduction Example 20 was used in place of the polymer emulsion particle(TB-1). The initial contact angle of the obtained test plate (G-9)having an organic/inorganic composite film with water was 7.2°.

The results of Examples and Comparative Examples are shown in Table 16.

TABLE 16 Contact angle Content of after high- Heat aqueous- temperature/Initial curing phase high-humidity contact time component test angle(hr) (mass %) (°) (°) Example 79 15 2.76 11 7 Example 80 8 4.57 13 7Example 81 4 8.91 15 7 Example 82 3.5 11.46 23 7 Example 83 3 14.12 31 7Example 84 2.5 16.34 42 7 Example 85 2 18.19 47 7 Comparative 1 21.93 527 Example 12 Comparative 0 28.66 55 7 Example 13

As shown in Table 16, it was demonstrated that the coating films ofExamples can maintain surface hydrophilicity at least even at hightemperature/high humidity.

The present application is based on Japanese Patent Application No.2009-058665 filed on Mar. 11, 2009 with the Japanese Patent Office,Japanese Patent Application No. 2009-270364 filed on Nov. 27, 2009 withthe Japanese Patent Office, Japanese Patent Application No. 2009-270375filed on Nov. 27, 2009 with the Japanese Patent Office and JapanesePatent Application No. 2010-045505 filed on Mar. 2, 2010 with theJapanese Patent Office and the contents thereof are incorporated hereinby reference.

INDUSTRIAL APPLICABILITY

The coating film and coating composition according to the presentinvention are excellent in antifouling properties, transparency,hydrophilicity and durability (shock resistance) and maintain surfacehydrophilicity even at high temperature/high humidity and thus used as amember of various energy production apparatuses and the like such as asolar cell module and a solar thermal power generation system, and canbe preferably used as a member having excellent transmittance ofsunlight and sunlight harvesting properties such as a protective memberof a solar cell and a member of a light reflecting mirror for solarthermal power generation.

REFERENCE SIGNS LIST

-   1 . . . Laminate-   10 . . . Substrate-   12 . . . Coating film-   2 . . . Solar cell module-   20 . . . Protective member-   22 . . . Backsheet-   24 . . . Power generating element-   26 . . . Sealant-   202 . . . Substrate-   204 . . . Coating film-   3 . . . Reflector device-   30 . . . Laminate (protective member)-   32 . . . Light reflecting mirror-   34 . . . Support

1. A coating composition comprising (A) a metal oxide particle having anumber average particle size of 1 nm to 400 nm, and (B) a polymerparticle, wherein a content of an aqueous-phase component in thecomponent (B), represented by the following expression (I), is 20 mass %or less:The content of the aqueous-phase component (%)=(dry mass of a filtrateobtained by filtering the component (B) at a molecular cutoff of50,000)×(100−total mass of solid content)/(mass of the filtrate−dry massof the filtrate)×100/the total mass of solid content  (I).
 2. Thecoating composition according to claim 1, wherein the component (B) is apolymer emulsion particle (B1) obtained, in a polymerization materialsolution comprising a component (b1): a hydrolyzable silicon compound, acomponent (b2): a vinyl monomer, a component (b3): an emulsifier, and acomponent (b4): water, by polymerizing the component (b1) and thecomponent (b2).
 3. The coating composition according to claim 1 or 2,wherein the content of the aqueous-phase component is 15 mass % or less.4. The coating composition according to claim 1 or 2, wherein thecomponent (B) has a number average particle size of 10 nm to 800 nm. 5.The coating composition according to claim 2, wherein the component (b2)is a vinyl monomer having at least one functional group selected fromthe group consisting of a hydroxy group, a carboxyl group, an amidegroup, an amino group and an ether group.
 6. The coating compositionaccording to claim 2, wherein a mass ratio ((b2)/(B)) of the component(b2) to the component (B) is 0.01/1 to 1/1.
 7. The coating compositionaccording to claim 2, wherein a mass ratio ((b2)/(A)) of the component(b2) to the component (A) is 0.01/1 to 1/1.
 8. The coating compositionaccording to claim 1 or 2, wherein the component (B) has a core/shellstructure comprising a core layer and one or two or more shell layerscovering the core layer.
 9. The coating composition according to claim8, wherein a mass ratio ((b2)/(b1)) of the component (b2) to thecomponent (b1) in the core layer is 0.01/1 to 1/1, and the mass ratio((b2)/(b1)) of the component (b2) to the component (b1) in an outermostlayer of the shell layers is 0.01/1 to 5/1.
 10. The coating compositionaccording to claim 8, wherein the component (B) is a polymer emulsionparticle obtained by polymerizing the polymerization material solutionin the presence of a seed particle forming the core layer, and the seedparticle is obtained by polymerizing at least one component selectedfrom the group consisting of the component (b1), the component (b2) anda component (b5): another vinyl monomer copolymerizable with thecomponent (b2).
 11. The coating composition according to claim 2,wherein the component (b2) is a vinyl monomer having a secondary amidegroup, a tertiary amide group or both of those.
 12. The coatingcomposition according to claim 1 or 2, wherein a mass ratio ((A)/(B)) ofthe component (A) to the component (B) is 110/100 to 480/100.
 13. Thecoating composition according to claim 1 or 2, further comprising acomponent (C): at least one hydrolyzable silicon compound selected fromthe group consisting of compounds represented by the following formulas(1), (2) and (3):R¹ _(n)SiX_(4-n)  (1) wherein R¹ represents a hydrogen atom, or an alkylgroup, alkenyl group, alkynyl group or aryl group having 1 to 10 carbonatoms and optionally having a halogen group, a hydroxy group, a mercaptogroup, an amino group, a (meth)acryloyl group or an epoxy group; Xrepresents a hydrolyzable group; and n is an integer of 0 to 3.X₃Si—R² _(n)—SiX₃  (2) wherein X represents a hydrolyzable group; R²represents an alkylene group or phenylene group having 1 to 6 carbonatoms; and n is 0 or 1.R³—(O—Si(OR³)₂)_(n)—OR³  (3) wherein R³ represents an alkyl group having1 to 6 carbon atoms; and n is an integer of 2 to
 8. 14. The coatingcomposition according to claim 13, wherein a mass ratio ((C)/(A)) of thecomponent (C) to the component (A) is 1/100 to 150/100.
 15. (canceled)16. The coating composition according to claim 1 or 2, wherein thecomponent (A) comprises a component (A1): silica having a number averageparticle size of 1 nm to 400 nm, and a component (A2): an infraredabsorbent having a number average particle size of 1 nm to 2000 nm; amass ratio ((A1+A2)/(B)) of a total content of the component (A1) andthe component (A2) to a content of the component (B) is 60/100 to1000/100; and a mass ratio ((A2)/(A1+B)) of the content of the component(A2) to a total content of the component (B) and the component (A1) is0.05/100 to 40/100.
 17. The coating composition according to claim 1 or2, wherein the component (A) comprises a component (A1): silica having anumber average particle size of 1 nm to 400 nm, and a component (A3): aphotocatalyst having a number average particle size of 1 nm to 2000 nm;a mass ratio ((A1+A3)/(B)) of a total content of the component (A1) andthe component (A3) to a content of the component (B) is 60/100 to480/100; and a mass ratio ((A1)/(A1+A3)) of a content of the component(A1) to the total content of the component (A1) and the component (A3)is 85/100 to 99/100.
 18. (canceled)
 19. (canceled)
 20. (canceled) 21.(canceled)
 22. (canceled)
 23. A coating film obtained from the coatingcomposition according to claim 1 or
 2. 24. A coating film comprising (A)a metal oxide particle and (B) a polymer particle surrounded by thecomponent (A), wherein a film formed of a component (B2) having amolecular cutoff of 50,000 or less and extracted from the component (B)by ultrafiltration has a surface water contact angle of 30° or less. 25.A coating film comprising (A) a metal oxide particle having a numberaverage particle size of 1 nm to 400 nm, and (B) a polymer particlesurrounded by the component (A), wherein a film formed of a component(B2) having a molecular cutoff of 50,000 or less and extracted from thecomponent (B) by ultrafiltration has a surface water contact angle ofmore than 30° and the content thereof is 5 mass % or less.
 26. Thecoating film according to claim 24 or 25, wherein the component (B) isan emulsion particle.
 27. The coating film according to claim 24 or 25,having a surface water contact angle at 20° C. of 30° or less.
 28. Thecoating film according to claim 24 or 25, wherein the coating film aftera high-temperature/high-humidity test in which the coating film isallowed to stand still for 24 hours under the conditions of atemperature of 90° C. and a humidity of 90% has a surface water contactangle of 20° or less.
 29. A laminate comprising a substrate and acoating film obtained by applying the coating composition according toclaim 1 or 2 or the coating film according to claim 24 or 25 and formedon at least one of surfaces of the substrate.
 30. The laminate accordingto claim 29, having a light transmittance higher than a lighttransmittance of the substrate.
 31. The laminate according to claim 29,wherein the coating film has a refractive index 0.1 or more lower than arefractive index of the substrate.
 32. The laminate according to claim29, wherein the coating film has two or more layers.
 33. The laminateaccording to claim 32, wherein an outermost layer positioned on anopposite side of the substrate has a refractive index 0.1 or more lowerthan a refractive index of a layer adjacent to the outermost layer. 34.The laminate according to claim 32, wherein layers constituting thecoating film each have a thickness (dn) of 10 nm to 800 nm and a totalthickness (Σdn) of the coating film is 100 nm to 4000 nm.
 35. Thelaminate according to claim 29, wherein the substrate has a lighttransmittance of 30% to 99%.
 36. The laminate according to claim 29,wherein a ratio ((Rc)/(Rb)) of a reflectivity (Rc) of an oppositesurface to the substrate of the coating film to a reflectivity (Rb) ofthe surface of the substrate on a coating film side is 98% or more. 37.The laminate according to claim 29, wherein the difference in refractiveindex between the coating film and the substrate is 0.2 or less.
 38. Thelaminate according to claim 29, wherein the coating film has arefractive index of 1.30 to 1.48.
 39. The laminate according to claim36, wherein the surface of the substrate on the coating film side hasthe reflectivity (Rb) of 80% or more.
 40. The laminate according toclaim 29, wherein the substrate comprises at least one substanceselected from the group consisting of glass, an acrylic resin, apolycarbonate resin, a cyclic olefin resin, a polyethylene terephthalateresin and an ethylene-fluoroethylene copolymer.
 41. A method formanufacturing a laminate, comprising the steps of: forming a coatingfilm by applying the coating composition according to claim 1 or 2 on atleast one of surfaces of a substrate, and applying at least one of athermal treatment at 70° C. or more and a pressurization treatment at0.1 kPa or more to the coating film.
 42. The laminate according to claim29, which is a member for use in an energy conversion apparatus. 43.(canceled)
 44. A solar cell module comprising the laminate according toclaim 42, a backsheet arranged so as to face the laminate, and anelectric power generating element arranged between the laminate and thebacksheet.
 45. The laminate according to claim 42, which is a protectivemember for a light reflecting mirror.
 46. A reflector device comprisinga light reflecting mirror, the laminate according to claim 45 forprotecting a reflection surface of the light reflecting mirror, and asupport for supporting the reflecting mirror.
 47. (canceled)